CN103924261A - Preparation method for oxygen evolution electrode based on graphene oxide reduction - Google Patents
Preparation method for oxygen evolution electrode based on graphene oxide reduction Download PDFInfo
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- CN103924261A CN103924261A CN201410155738.5A CN201410155738A CN103924261A CN 103924261 A CN103924261 A CN 103924261A CN 201410155738 A CN201410155738 A CN 201410155738A CN 103924261 A CN103924261 A CN 103924261A
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Abstract
The invention discloses a preparation method for an oxygen evolution electrode based on graphene oxide reduction. The method comprises the following steps: 1) oxidizing graphite power to prepare graphite oxide; 2) carrying out ultrasonic treatment on the graphite oxide prepared in the step 1) to prepare graphene oxide; 3) adding water to dilute the graphite oxide prepared in the step 2); 4) carrying out a hydrothermal reduction reaction on the diluted graphite oxide solution obtained in the step 3), thus obtaining a product, namely the oxygen evolution electrode based on graphene oxide reduction. The oxygen evolution electrode based on graphene oxide reduction prepared in the invention has excellent oxygen evolution catalytic performance and long-term stability, can replace expensive iridium and oxide electrode thereof, can be widely applied to the field of water and metal-air photolysis batteries and other energy conversion devices and the like, and has relatively high practical value. The common graphite power is adopted as a raw material in the invention, the raw material source is wide, the price is low, and the preparation method is simple and is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of oxygen and separate out the preparation method of electrode, be specifically related to a kind of oxygen based on reduced graphene oxide serving and separate out the preparation method of electrode.
Background technology
The evolution reaction of oxygen is one of most important electrocatalytic reaction, is widely used in the fields such as photodissociation water and metal-air battery.Iridium and oxide electrode thereof are that the traditional electrode of current oxygen evolution reaction is also the most frequently used electrode, but iridium is as precious metal, its expensive, resource-constrained, and performance loss is serious during long-play, has hindered the commercialized development in the fields such as photodissociation water and metal-air battery.The wretched insufficiency such as when, resource-constrained expensive for iridium and oxide electrode thereof, long-play performance loss is serious, Recent study finds that some transition metal (for example cobalt and nickel) oxide material shows certain oxygen and separates out performance, but transition metal oxide oxygen Evolution overpotential is conventionally higher, effect is undesirable, and complex steps, is difficult to realize scale operation.For example:
a Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles. Jin Suntivich et al. Science 334,1383 (2011). DOI:10.1126/science.1212858; An Advanced Ni-Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation. Ming Gong et al. J. Am. Chem. Soc. 135,8452 (2013). DOI:10.1021/ja4027715; Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nature Communications 4,2390 (2013). DOI:10.1038/ncomms3390.
Therefore, study a kind of efficient, low price, reliable and stable, the simple oxygen of preparation process is separated out electrode and is seemed very necessary.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of oxygen based on reduced graphene oxide serving to separate out the preparation method of electrode, this electrode has good oxygen and separates out catalytic performance and permanent stability, and starting material source is abundant, preparation method is simple, cheap.
For achieving the above object, the invention provides following technical scheme:
Oxygen based on reduced graphene oxide serving of the present invention is separated out the preparation method of electrode, comprises the following steps:
1) Graphite Powder 99 is oxidized and prepares graphite oxide;
2) graphite oxide of being prepared by step 1) carries out supersound process and prepares graphene oxide;
3) by step 2) the graphene oxide thin up prepared;
4) the graphene oxide solution after dilution step 3) being obtained carries out hydrothermal reduction reaction, and the oxygen that the product obtaining is based on reduced graphene oxide serving is separated out electrode.
Further, in described step 1), use the vitriol oil, SODIUMNITRATE and potassium permanganate that Graphite Powder 99 is oxidized, prepare graphite oxide.
Further, described step 2) in, by graphite oxide supersound process 6 ~ 24h at 4 ~ 50 ℃, prepare graphene oxide.
Further, the graphene oxide strength of solution after the dilution that described step 3) obtains is 0.1 ~ 1.0 mg/ml.
Further, in described step 4), hydrothermal reduction temperature of reaction is 120 ~ 200 ℃, and the reaction times is 6 ~ 24h.
Beneficial effect of the present invention is:
The present invention by graphite oxidation and ultrasonic after obtain graphene oxide, then graphene oxide is diluted, finally by the oxygen that hydrothermal reduction reaction is prepared based on reduced graphene oxide serving excessively, separate out electrode, the experiment proved that, this electrode has good oxygen and separates out catalytic performance and permanent stability, and raw material of the present invention is common graphite powder, raw material sources are extensive, cheap, preparation method simple, be applicable to scale operation.
Graphene is a kind of novel material of the individual layer sheet structure consisting of carbon atom, is a kind ofly by carbon atom, with sp2 hybridized orbital, to form the flat film that hexangle type is honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Since the physicist An Deliehaimu of Univ Manchester UK in 2004 and Constantine Nuo Woxiaoluofu successfully isolate Graphene in experiment from graphite, Graphene, because of its good conductivity, light transmission and flex capability having, makes it in fields such as touch-screen, liquid-crystal display, organic photovoltaic battery, Organic Light Emitting Diodes, as transparent electrical conducting electrode, be widely used.And having efficient oxygen, the reduced graphene oxide serving of being prepared by method of the present invention separates out catalytic performance, can be used as oxygen and separate out electrode use, thereby expanded the range of application of Graphene, oxygen based on reduced graphene oxide serving prepared by the present invention is separated out iridium and the oxide electrode thereof of the alternative costliness of electrode, and be widely used in the fields such as photodissociation water and metal-air battery and other energy conversion apparatus, possess higher practical value.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearer, the invention provides following accompanying drawing and describe:
Fig. 1 is the transmission electron microscope picture of the reduced graphene oxide serving electrode of embodiment 1 preparation;
Fig. 2 is reduced graphene oxide serving electrode and the polarization curve comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation;
Fig. 3 is reduced graphene oxide serving electrode and the stability comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation;
Fig. 4 is the transmission electron microscope picture of the reduced graphene oxide serving electrode of embodiment 2 preparations;
Fig. 5 is reduced graphene oxide serving electrode and the polarization curve comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations;
Fig. 6 is reduced graphene oxide serving electrode and the stability comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
The oxygen based on reduced graphene oxide serving of the present embodiment is separated out the preparation method of electrode, comprises the following steps:
1) use the vitriol oil, SODIUMNITRATE and potassium permanganate that Graphite Powder 99 is oxidized, prepare graphite oxide;
2) graphite oxide of being prepared by step 1) is supersound process 10h at 10 ℃, prepares graphene oxide;
3) by step 2) to be diluted with water to concentration be 0.5 mg/ml for the graphene oxide prepared;
4) the graphene oxide solution after dilution step 3) being obtained is hydrothermal reduction reaction 12h at 180 ℃, and the oxygen that the product obtaining is based on reduced graphene oxide serving is separated out electrode.
Fig. 1 is the transmission electron microscope picture of the reduced graphene oxide serving electrode of embodiment 1 preparation; From figure, can find out clearly the reduced graphene oxide serving structure of sheet.
Fig. 2 is reduced graphene oxide serving electrode and the polarization curve comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation, find to compare with iridium oxide/carbon dioxide process carbon electrode, reduced graphene oxide serving electrode shows more negative take-off potential, illustrates that reduced graphene oxide serving electrode has efficient oxygen and separates out catalytic performance.
Fig. 3 is reduced graphene oxide serving electrode and the stability comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation, find to compare with iridium oxide/carbon dioxide process carbon electrode, after operation 4000s, reduced graphene oxide serving electrode has more negative current potential 1.46 V, than iridium oxide/carbon dioxide process carbon electrode current potential, improved about 57mV, illustrate that reduced graphene oxide serving electrode is more suitable for long-term operation, has higher stability.
Above-mentioned experimental data shows, the reduced graphene oxide serving electrode of embodiment 1 preparation has good oxygen and separates out catalytic performance and permanent stability, and the iridium of alternative costliness and oxide electrode thereof are separated out electrode as oxygen and used.
embodiment 2
The oxygen based on reduced graphene oxide serving of the present embodiment is separated out the preparation method of electrode, comprises the following steps:
1) use the vitriol oil, SODIUMNITRATE and potassium permanganate that Graphite Powder 99 is oxidized, prepare graphite oxide;
2) graphite oxide of being prepared by step 1) is supersound process 12h at 15 ℃, prepares graphene oxide;
3) by step 2) to be diluted with water to concentration be 1.0mg/ml for the graphene oxide prepared;
4) the graphene oxide solution after dilution step 3) being obtained is hydrothermal reduction reaction 10h at 200 ℃, and the oxygen that the product obtaining is based on reduced graphene oxide serving is separated out electrode.
Fig. 4 is the transmission electron microscope picture of the reduced graphene oxide serving electrode of embodiment 2 preparations; From figure, can find out clearly the reduced graphene oxide serving structure of sheet.
Fig. 5 is reduced graphene oxide serving electrode and the polarization curve comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations, find to compare with iridium oxide/carbon dioxide process carbon electrode, reduced graphene oxide serving electrode shows more negative take-off potential, illustrates that reduced graphene oxide serving electrode has efficient oxygen and separates out catalytic performance.
Fig. 6 is reduced graphene oxide serving electrode and the stability comparison diagram of iridium oxide/carbon dioxide process carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations, find to compare with iridium oxide/carbon dioxide process carbon electrode, after operation 3000s, reduced graphene oxide serving electrode has more negative current potential 1.48 V, than iridium oxide/carbon dioxide process carbon electrode current potential, improved about 48mV, illustrate that reduced graphene oxide serving electrode is more suitable for long-term operation, has higher stability.
Above-mentioned experimental data shows, the reduced graphene oxide serving electrode of embodiment 2 preparations has good oxygen and separates out catalytic performance and permanent stability, and the iridium of alternative costliness and oxide electrode thereof are separated out electrode as oxygen and used.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can to it, make various changes in the form and details, and not depart from the claims in the present invention book limited range.
Claims (5)
1. the oxygen based on reduced graphene oxide serving is separated out the preparation method of electrode, it is characterized in that: comprise the following steps:
1) Graphite Powder 99 is oxidized and prepares graphite oxide;
2) graphite oxide of being prepared by step 1) carries out supersound process and prepares graphene oxide;
3) by step 2) the graphene oxide thin up prepared;
4) the graphene oxide solution after dilution step 3) being obtained carries out hydrothermal reduction reaction, and the oxygen that the product obtaining is based on reduced graphene oxide serving is separated out electrode.
2. the oxygen based on reduced graphene oxide serving according to claim 1 is separated out the preparation method of electrode, it is characterized in that: in described step 1), use the vitriol oil, SODIUMNITRATE and potassium permanganate that Graphite Powder 99 is oxidized, prepare graphite oxide.
3. the oxygen based on reduced graphene oxide serving according to claim 1 is separated out the preparation method of electrode, it is characterized in that: described step 2), by graphite oxide supersound process 6 ~ 24h at 4 ~ 50 ℃, prepare graphene oxide.
4. the oxygen based on reduced graphene oxide serving according to claim 1 is separated out the preparation method of electrode, it is characterized in that: the graphene oxide strength of solution after the dilution that described step 3) obtains is 0.1 ~ 1.0 mg/ml.
5. the oxygen based on reduced graphene oxide serving according to claim 1 is separated out the preparation method of electrode, it is characterized in that: in described step 4), hydrothermal reduction temperature of reaction is 120 ~ 200 ℃, and the reaction times is 6 ~ 24h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104746097A (en) * | 2015-04-28 | 2015-07-01 | 中国船舶重工集团公司第七二五研究所 | Preparation method of graphene-doped metallic oxide anode |
| CN104966842A (en) * | 2015-06-05 | 2015-10-07 | 清华大学 | Water oxidation catalyst based on porous carbon material and preparation method thereof |
| CN110230072A (en) * | 2019-05-06 | 2019-09-13 | 湖北大学 | A kind of preparation method and application of the N-NiZnCu LDH/rGO nano-chip arrays material in nickel foam |
| CN110707319A (en) * | 2019-09-27 | 2020-01-17 | 上海应用技术大学 | Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof |
| CN111250073A (en) * | 2020-02-18 | 2020-06-09 | 北京科技大学 | Preparation method of graphene electrocatalyst with hierarchical pore channel three-dimensional structure |
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| EP0443259B1 (en) * | 1990-02-05 | 1996-05-01 | Westinghouse Electric Corporation | Solid oxide electrochemical oxygen generator |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
| CN102839388A (en) * | 2012-09-05 | 2012-12-26 | 中国科学院上海微***与信息技术研究所 | Graphene/molybdenum disulfide composite electrode material and preparation method thereof |
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Patent Citations (3)
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| EP0443259B1 (en) * | 1990-02-05 | 1996-05-01 | Westinghouse Electric Corporation | Solid oxide electrochemical oxygen generator |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746097A (en) * | 2015-04-28 | 2015-07-01 | 中国船舶重工集团公司第七二五研究所 | Preparation method of graphene-doped metallic oxide anode |
| CN104966842A (en) * | 2015-06-05 | 2015-10-07 | 清华大学 | Water oxidation catalyst based on porous carbon material and preparation method thereof |
| CN104966842B (en) * | 2015-06-05 | 2018-08-28 | 清华大学 | A kind of water oxidation reaction catalyst and preparation method thereof based on porous carbon materials |
| CN110230072A (en) * | 2019-05-06 | 2019-09-13 | 湖北大学 | A kind of preparation method and application of the N-NiZnCu LDH/rGO nano-chip arrays material in nickel foam |
| CN110707319A (en) * | 2019-09-27 | 2020-01-17 | 上海应用技术大学 | Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof |
| CN111250073A (en) * | 2020-02-18 | 2020-06-09 | 北京科技大学 | Preparation method of graphene electrocatalyst with hierarchical pore channel three-dimensional structure |
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