CN108314016A - One kind is based on redox graphene and preparation method thereof - Google Patents
One kind is based on redox graphene and preparation method thereof Download PDFInfo
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- CN108314016A CN108314016A CN201810377161.0A CN201810377161A CN108314016A CN 108314016 A CN108314016 A CN 108314016A CN 201810377161 A CN201810377161 A CN 201810377161A CN 108314016 A CN108314016 A CN 108314016A
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- graphene
- cuprous
- redox graphene
- deionized water
- hydrochloric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
The present invention provides one kind being based on redox graphene comprising：Graphene oxide 0.01 0.2%；Cuprous halide 0.1 0.3%；Concentrated hydrochloric acid 6.4 10%；Deionized water 89.69 93.3%.The present invention also provides a kind of preparation methods based on redox graphene comprising：1) cuprous halide is add to deionized water, and concentrated hydrochloric acid is added thereto, until forming cuprous halide solution；2) graphene oxide is scattered in deionized water, supersound process forms graphene oxide dispersion, and cuprous halide solution is added, is heated；3) vacuum pumping rate is carried out, is washed to neutrality, is put into baking oven and dries, obtain graphene.The present invention has stronger reproducibility compared to the prior art, can significantly improve the ratio of C/O in graphene, it is easy to accomplish the industrialized production of graphene, while environmentally protective and reaction condition is mild.
Description
Technical field
The present invention relates to technical field of graphene, and redox graphene and its system are based in particular to one kind
Preparation Method.
Background technology
Currently, the preparation method of graphene mainly include micromechanics stripping method, chemical vapour deposition technique, ion insertion method and
Oxidation-reduction method etc..
2004, the An Deliehaimu and Constantine's Nuo Woxiao loves of Univ Manchester UK were shelled using micromechanics
It prepares and has observed single-layer graphene for the first time from method, obtain Nobel Prize in physics in 2010.But the method yield
It is inexpensive high, it is unsatisfactory for the requirement of industrialization and large-scale production.
Chemical vapour deposition technique refers to passing through high temperature by gases such as CH4, CO, and carbon atom is deposited in substrate surface, is generated
Two-dimensional graphene film, but the method needs high temperature, high energy consumption, and graphene to peel off from the substrate low yield, cost
Height cannot meet industrial production demand.
Then ion insertion method is dispersed in organic solution firstly the need of compound between graphite layers are prepared and prepares graphite
The smaller quality of graphene film damage layer of alkene, the method production is high, but graphene dispersion degree is relatively low.
Oxidation-reduction method is considered as the industrialized optimal path of realization since method is simple and practicable, and stone in the prior art
The restoring method of black alkene be mainly hydrazine hydrate, sodium borohydride, Dimethylhydrazine, high temperature thermal reduction etc., these methods or have high toxicity,
Or reaction needs high temperature, and reaction condition is complicated, it is difficult to realize industrialized production.
Invention content
In consideration of it, the present invention provides one kind based on redox graphene and preparation method thereof, can meet it is nontoxic,
The requirement that environmentally protective, reaction condition is mild, can be mass-produced.
On the one hand, the present invention provides one kind being based on redox graphene comprising the group of following weight percent
Point：
Further, above-mentioned one kind includes following components in percentage by weight based on redox graphene：Aoxidize stone
Black alkene 0.05-0.1%；Cuprous halide 0.15-0.2%；Concentrated hydrochloric acid 7.6-9%；Deionized water 90.75-92.15%.
Further, above-mentioned one kind includes following components in percentage by weight based on redox graphene：Aoxidize stone
Black alkene 0.08-0.1%；Cuprous halide 0.17-0.2%；Concentrated hydrochloric acid 8-8.95%；Deionized water 90.75-91.75%.
Further, above-mentioned one kind includes following components in percentage by weight based on redox graphene：Aoxidize stone
Black alkene 0.09%；Cuprous halide 0.18%；Concentrated hydrochloric acid 8.5%；Deionized water 91.23%.
On the other hand, the present invention provides a kind of preparation methods based on redox graphene comprising：
1) according to above-mentioned proportioning, cuprous halide is added at least 1/6th deionized water, and added thereto
Enter concentrated hydrochloric acid, until solid is completely dissolved, forms cuprous halide solution；
2) according to above-mentioned proportioning, graphene oxide is scattered at least 5/6ths deionized water, is ultrasonically treated
Graphene oxide dispersion is formed, then the rear cuprous halide solution that step 1) is added and prepares is heated；
3) product of step 2) is subjected to vacuum pumping rate, with, again with pure water to neutrality, being put into baking oven after salt acid elution
Middle drying, finally obtains graphene.
Further, above-mentioned cuprous halide is stannous chloride, cuprous bromide or cuprous iodide.
Further, the power of above-mentioned supersound process is 150-1200W, and the time of supersound process is -4 hours 20 minutes.
Further, above-mentioned steps 2) in, heating temperature is 40-100 DEG C, and heating time is 4-24 hours.
Further, above-mentioned steps 3) in, a concentration of 5-10% of hydrochloric acid.
Further, above-mentioned steps 3) in, drying mode is vacuum drying, spray drying or forced air drying.
Further, above-mentioned drying temperature is 40-100 DEG C, and drying time is 5-72 hours.
The present invention mainly has the following advantages compared to the prior art：
1) nontoxic and environmentally protective using cuprous halide as reducing agent；
2) reaction condition is mild；
3) using cuprous halide as reducing agent, there is stronger reproducibility, the ratio of C/O in graphene can be significantly improved,
It is easily achieved the industrialized production of graphene.
Description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit are common for this field
Technical staff will become clear.Attached drawing only for the purpose of illustrating preferred embodiments, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the graphene prepared by the embodiment of the present invention.
Fig. 2 is the XPS collection of illustrative plates of graphene oxide and graphene after reduction in the embodiment of the present invention.
Fig. 3 is the infared spectrum of graphene oxide and graphene after reduction in the embodiment of the present invention.
Specific implementation mode
The exemplary embodiment of the disclosure is described in more detail below.Although attached drawing shows the exemplary reality of the disclosure
Apply example, it being understood, however, that may be realized in various forms the disclosure without should be limited by embodiments set forth here.Phase
Instead, these embodiments are provided to facilitate a more thoroughly understanding of the present invention, and can completely pass the scope of the present disclosure
Up to those skilled in the art.
Embodiment one：
It weighs 150mg cuprous bromides to be added in 20ml deionized waters (being specifically as follows distilled water), and is added thereto
9ml concentrated hydrochloric acids are all dissolved to cuprous bromide；It is water-soluble that it can be configured to the cuprous halide that mass percent is 0.1-0.5%
Liquid；
It weighs 0.1g graphene oxides to be added in 100ml deionized waters (being specifically as follows distilled water), in 150-1200W
Ultrasound is added 100 DEG C of cuprous bromide aqueous solution and is stirred at reflux reaction 4 hours after 30 minutes under the conditions of (preferably 900W)；It can
Mass fraction is formed as the uniform dispersion liquids of 0.01-0.2% with processing；The specific preparation method of this step can be Hummers,
One kind in Brodie, Staudenmaier method, preferably Hummers methods；
Through 5% hydrochloric acid and distillation water washing, it is put into baking oven and dries 12 hours for 50 DEG C.
At this point, test C/O atomic ratios are 5.1.
Embodiment two：
It weighs 190mg cuprous iodides to be added in 20ml deionized waters (being specifically as follows distilled water), and is added thereto
10ml concentrated hydrochloric acid values cuprous iodide all dissolves；
It weighs 0.1g graphene oxides to be added in 100ml deionized waters (being specifically as follows distilled water), under the conditions of 900W
Ultrasound is added 100 DEG C of cuprous iodide aqueous solution and is stirred at reflux reaction 4 hours after 30 minutes；
Through 5% hydrochloric acid and distillation water washing, it is put into 50 DEG C of drying in baking oven and stays overnight.
Embodiment three：
300mg cuprous bromides are weighed first to be added in 20ml distilled water, and 10ml concentrated hydrochloric acids are added thereto to bromination
Cuprous all dissolvings；
It weighs 20mg graphene oxides to be added in 100ml distilled water, bromine is added after 4 hours in ultrasound under the conditions of 150W
Change the 40 DEG C of reactions of cuprous aqueous solution overnight；
Most it is put into 100 DEG C of baking ovens and dries 5 hours through 10% hydrochloric acid and distillation water washing afterwards.
Example IV：
300mg cuprous bromides are weighed first to be added in 20ml distilled water, and 10ml concentrated hydrochloric acids are added thereto to bromination
Cuprous all dissolvings；
It weighs 20mg graphene oxides to be added in 100ml distilled water, bromine is added after 4 hours in ultrasound under the conditions of 150W
Change the 60 DEG C of reactions of cuprous aqueous solution；
Most it is put into 100 DEG C of baking ovens and dries 5 hours through 10% hydrochloric acid and distillation water washing afterwards.
Other embodiment：
| Embodiment | Proportioning |
| 5 | Graphene oxide 0.2%；Cuprous halide 0.1%；Concentrated hydrochloric acid 6.4%；Deionized water 93.3% |
| 6 | Graphene oxide 0.01%；Cuprous halide 0.3%；Concentrated hydrochloric acid 10%；Deionized water 89.69% |
| 7 | Graphene oxide 0.1%；Cuprous halide 0.15%；Concentrated hydrochloric acid 9%；Deionized water 90.75% |
| 8 | Graphene oxide 0.05%；Cuprous halide 0.2%；Concentrated hydrochloric acid 7.6%；Deionized water 92.15% |
| 9 | Graphene oxide 0.08%；Cuprous halide 0.17%；Concentrated hydrochloric acid 8%；Deionized water 91.75% |
| 10 | Graphene oxide 0.1%；Cuprous halide 0.2%；Concentrated hydrochloric acid 8.95%；Deionized water 90.75% |
| 11 | Graphene oxide 0.09%；Cuprous halide 0.18%；Concentrated hydrochloric acid 8.5%；Deionized water 91.23% |
The preparation method of above-described embodiment is identical as described in embodiment one to four, and details are not described herein.
It is as follows referring now to being carried out to the effect of above-described embodiment for the present embodiment 1 since gained graphene performance is similar
Analysis：
As shown in Figure 1, the graphene prepared in embodiment SEM figure, graphene be in gauze-like, illustrate graphene number of plies compared with
Few, quality is higher；
As shown in Fig. 2, in embodiment GO and r-GO C1sXPS spectrograms.Absorption peak corresponds to C-C keys and C=C at 284.8ev
The combination of key can characteristic signal peak, the places 286.2ev absorption peak corresponds to the characteristic signal peak of the combination energy of C-O keys, at 287.8ev
Absorption peak corresponds to the characteristic signal peak of the combination energy of C=O keys.After GO is handled by embodiment one, the C-C keys and C=C of rGO are bonded
The characteristic signal peak for closing energy is remarkably reinforced, and the characteristic signal peak of C-O bonding energies obviously weakens, this illustrates the sp2 knots of graphene
Structure has obtained part and has restored.
As shown in figure 3, in embodiment GO and r-GO infrared spectrum, the absorption peak occurred at wherein 1052cm-1 is O-C-
The stretching vibration peak of O；Absorption peak corresponds to the deformation absorption peak of hydroxyl O-H at 1390cm-1；Absorption peak belongs at 1620cm-1
In the deformation vibration the absworption peak of adsorbed water molecule, this illustrates although graphite oxide is frozen drying, but still has Water Molecular Adsorption,
This is because graphite oxide has certain hygroscopicity；At 1720cm-1 absorption peak be carbonyl C=0 stretching vibration absworption peak and
The stretching vibration absworption peak of carboxyl O=C-OH；The relatively strong wider absorption peak that 3400cm-1 or so occurs is the flexible of hydroxyl O-H
Vibration peak.Be indicated above graphite powder it is oxidized after, the functions such as a large amount of hydroxyl, carbonyl, carboxyl, epoxy group are inserted in lamella
Group.After method processing in embodiment 2, the feature peak intensity of all oxygen-containing functional groups all obviously weakens in r-GO, almost disappears.
This shows that most of oxygen-containing functional group is all removed in GO, and GO, which is reduced, generates high-quality graphene.
To sum up, above-described embodiment mainly has the following advantages compared to the prior art：
1) nontoxic and environmentally protective using cuprous halide as reducing agent；
2) reaction condition is mild；
3) using cuprous halide as reducing agent, there is stronger reproducibility, the ratio of C/0 in graphene can be significantly improved,
It is easily achieved the industrialized production of graphene.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. one kind being based on redox graphene, which is characterized in that including following components in percentage by weight：
2. according to claim 1 a kind of based on redox graphene, which is characterized in that including following weight percent
The component of ratio：Graphene oxide 0.05-0.1%；Cuprous halide 0.15-0.2%；Concentrated hydrochloric acid 7.6-9%；Deionized water 90.75-
92.15%.
3. according to claim 1 a kind of based on redox graphene, which is characterized in that including following weight percent
The component of ratio：Graphene oxide 0.08-0.1%；Cuprous halide 0.17-0.2%；Concentrated hydrochloric acid 8-8.95%；Deionized water
90.75-91.75%.
4. according to claim 1 a kind of based on redox graphene, which is characterized in that including following weight percent
The component of ratio：Graphene oxide 0.09%；Cuprous halide 0.18%；Concentrated hydrochloric acid 8.5%；Deionized water 91.23%.
5. a kind of preparation method based on redox graphene, it is characterised in that：Including：
1) according to any proportionings of claim 1-4, cuprous halide is added at least 1/6th deionized water,
And concentrated hydrochloric acid is added thereto, until solid is completely dissolved, form cuprous halide solution；
2) according to any proportionings of claim 1-4, graphene oxide is scattered in at least 5/6ths deionized water
In, supersound process forms graphene oxide dispersion, then the rear cuprous halide solution that step 1) is added and prepares is heated；
3) product of step 2) is subjected to vacuum pumping rate, with, again with pure water to neutrality, being put into baking oven and dry after salt acid elution
It is dry, finally obtain graphene.
6. a kind of preparation method based on redox graphene according to claim 5, it is characterised in that：The halogen
It is stannous chloride, cuprous bromide or cuprous iodide to change cuprous.
7. a kind of preparation method based on redox graphene according to claim 5, it is characterised in that：At ultrasound
The power of reason is 150-1200W, and the time of supersound process is -4 hours 20 minutes.
8. a kind of preparation method based on redox graphene according to claim 5, it is characterised in that：The step
It is rapid 2) in, heating temperature be 40-100 DEG C, heating time be 4-24 hours.
9. a kind of preparation method based on redox graphene according to claim 5, it is characterised in that：The step
It is rapid 3) in, a concentration of 5-10% of the hydrochloric acid.
10. a kind of preparation method based on redox graphene according to claim 5, it is characterised in that：It is described
In step 3), drying mode is vacuum drying, spray drying or forced air drying；
Preferably, drying temperature is 40-100 DEG C, and drying time is 5-72 hours.
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| CN201810377161.0A CN108314016A (en) | 2018-04-25 | 2018-04-25 | One kind is based on redox graphene and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557013A (en) * | 2010-12-28 | 2012-07-11 | 国家纳米科学中心 | Preparation method for reduced graphene oxide |
| US20180090802A1 (en) * | 2016-09-27 | 2018-03-29 | Samsung Electronics Co., Ltd. | Cathode and lithium air battery including the same, and method of preparing the cathode |
-
2018
- 2018-04-25 CN CN201810377161.0A patent/CN108314016A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557013A (en) * | 2010-12-28 | 2012-07-11 | 国家纳米科学中心 | Preparation method for reduced graphene oxide |
| US20180090802A1 (en) * | 2016-09-27 | 2018-03-29 | Samsung Electronics Co., Ltd. | Cathode and lithium air battery including the same, and method of preparing the cathode |
Non-Patent Citations (2)
| Title |
|---|
| CHANDRAMA SARKAR等: "Synthesis of copper oxide/reduced graphene oxide nanocomposite and its enhanced catalytic activity towards reduction of 4-nitrophenol†", 《RSC ADV.》 * |
| YOUCHENG ZHAO等: "A facile route to the synthesis copper oxide/reduced graphene oxide nanocomposites and electrochemical detection of catechol organic pollutant{", 《CRYSTENGCOMM》 * |
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Application publication date: 20180724 |