CN103435034A - Method for preparing graphene based non-metallic oxygen reduction catalyst - Google Patents
Method for preparing graphene based non-metallic oxygen reduction catalyst Download PDFInfo
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- CN103435034A CN103435034A CN2013103543217A CN201310354321A CN103435034A CN 103435034 A CN103435034 A CN 103435034A CN 2013103543217 A CN2013103543217 A CN 2013103543217A CN 201310354321 A CN201310354321 A CN 201310354321A CN 103435034 A CN103435034 A CN 103435034A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a method for preparing a graphene based non-metallic oxygen reduction catalyst. The graphene based non-metallic oxygen reduction catalyst is a graphene based oxygen reduction catalyst doped with non-metallic hetero-atom, the non-metallic hetero-atom comprises N, S, B and/or I, the method comprises the followings: oxidized graphene is prepared to be oxidized graphene solution with the concentration of 0.1 to 5 mg/ml; at the temperature of 70 to 120 DEG C, the oxidized graphene solution is stirred for 1 to 3 hours and then a reducing agent containing non-metallic hetero-atom is added, the temperature is kept to be 70 to 120 DEG C, stirring is performed continuously for 18 to 48 hours so as to achieve in-situ doping of the non-metallic hetero-atom during graphene reduction-oxidation; centrifugation, washing and drying are performed on the solid so as to obtain the graphene based non-metallic oxygen reduction catalyst.
Description
Technical field
The present invention relates to catalyzer, be specifically related to a kind of graphene-based nonmetal oxygen reduction catalyst and preparation method thereof.
Background technology
The energy is developing national economy and the important substance basis of uplifting the people's living standard, and is also an important restriction factor that directly affects Economic development.Along with economical and social development, the increase of population, the raising of living standards of the people, energy consumption will be growing.Meanwhile, due to endless exploitation and excavation, the fossil energy resource that the mankind depend on for existence now reduces gradually, and environmental pollution is on the rise.Reduce energy consumption, development of new clean energy, environmental contamination reduction, to energy science and technology, development proposes significant challenge.In Conversion of energy and field of storage, oxygen reduction reaction is a very important reaction.At many devices such as fuel cell, metal-air battery and water, purify, oxygen is surveyed and the process such as anticorrosion in, it more and more becomes a day by day serious bottleneck problem.At present, the catalyzer used in the hydrogen reduction process is the alloy catalyst of Pt/C and Pt.Yet due to Pt scarcity of resources, expensive, so such catalyzer has seriously limited the commercialization of fuel cell, metal-air battery etc.And the catalyst based cyclical stability of Pt is poor, hindered the lifting of battery performance.Therefore, find better cathod catalyst, the catalytic performance that improves electrode is the main direction of research.For cathod catalyst, research emphasis is the modified electrode structure on the one hand, improve the utilization ratio of catalyzer, on the other hand, Proton Exchange Membrane Fuel Cells is catalyzer mainly with noble metal, its high cost has restricted the industrialization of this clean energy, therefore seeks the base metal material of alternative catalyzer (for example carbon), has become one of major objective of fuel cell studies.
The carbon-based material of nonmetal doping becomes in oxygen reduction catalyst the most active class catalyzer of research, is expected to replace that Pt is catalyst based becomes cell cathode catalyzer of future generation.Wherein, Graphene is as a kind of two-dimensional material, because its unique structure and excellent physicochemical property have caused the concern of vast researcher.The nonmetal doping grapheme material, when can retain the excellent properties such as Graphene high conductivity, strong mechanical property, introduce active sites, becomes a kind of good oxygen reduction catalyst.
CN103145122A discloses a kind of preparation method of nitrogen-doped graphene, it makes nitrogen-doped graphene in the process that adopts the hydrazine hydrate reduction Graphene by 160～200 ℃ of lower hydro-thermal reactions, introducing nitrogen, the method treatment temp is still higher, and the heteroatoms mixed only limits to nitrogen.
Summary of the invention
The present invention aims to provide a kind of more easy, and treatment temp is lower, is applicable to the method for the graphene-based nonmetal oxygen reduction catalyst of the various heteroatomic preparation of doping.
At first the invention provides a kind of method for preparing graphene-based nonmetal oxygen reduction catalyst, the graphene-based oxygen reduction catalyst that described graphene-based nonmetal oxygen reduction catalyst is the nonmetallic heteroatoms doping, described nonmetallic heteroatoms comprises the reductive agents such as the corresponding ammoniacal liquor of N(), the reductive agent such as the corresponding sodium sulphite of S(), the reductive agent such as the corresponding NaBH4 of B() and/or the reductive agent such as the corresponding hydroiodic acid HI of I(), described method comprises:
It is 0.1～5mg/ml graphene oxide solution that graphene oxide is mixed with to concentration;
Under 70～120 ℃, described graphene oxide solution is stirred after 1～3 hour and is added the reductive agent that contains described nonmetallic heteroatoms, keep 70～120 ℃ continue to stir 18～48 hours so that when redox graphene in-situ doped described nonmetallic heteroatoms; And centrifugal, washing and dry gained solid make described graphene-based nonmetal oxygen reduction catalyst.
Method of the present invention is by the doping of Graphene reduction process situ N, S, B, I element, without the extra heteroatoms source of adding, such as nitrogenous source, ,Peng source, sulphur source and propiodal etc., applied widely, various doped graphenes can be provided, the catalyzer made has that the hydrogen reduction performance is good, the excellent properties such as have extended cycle life, hydrogen reduction catalytic performance and stability are preferably especially arranged under acidity or alkaline condition, can be applicable to the fields such as Proton Exchange Membrane Fuel Cells, direct methanol fuel cell and metal-air battery.In addition, method treatment temp of the present invention is low, and without high temperature sintering, whole process step in solution completes.
In the present invention, for being selected from least one in sodium sulphite, sodium borohydride, sodium bisulfite, ammonium sulfide, hydrazine hydrate and hydroiodic acid HI.The reductive agent convenient sources that the present invention is used, cheap and easy to get.
In a preferred example, described nonmetallic heteroatoms is S, and described reductive agent can be sodium sulphite and/or sodium pyrosulfate.
In another preferred example, described nonmetallic heteroatoms is S and N, and described reductive agent is ammonium sulfide.
Preferably, the mol ratio of described graphene oxide and reductive agent can be 1:(0.05～0.2).
Preferably, the concentration of described graphene oxide solution can be 0.5～1mg/ml.
Preferably, can prepare according to Hummer ' s method by described graphene oxide.
Preferably, the solvent for use of described graphene oxide solution can be water and/or ethanol.
The accompanying drawing explanation
The TEM photo that Fig. 1 is the graphene-based non-metallic catalyst of preparation graphene oxide used in the present invention;
The SEM photo of the graphene-based non-metallic catalyst of preparation graphene oxide used in Fig. 2 the present invention;
The SEM photo that Fig. 3 is embodiment 1 resulting sheet catalyst;
The SEM photo that Fig. 4 is embodiment 2 resulting bulk catalysts;
Fig. 5 is embodiment 1 gained cyclic voltammetry curve;
The volt-ampere curve that Fig. 6 is embodiment 1 gained circulation 1000 times;
Fig. 7 is embodiment 2 gained cyclic voltammetry curves;
The volt-ampere curve that Fig. 8 is embodiment 2 gained circulation 1000 times;
The energy spectrogram that Fig. 9 is embodiment 1 gained catalyzer;
The energy spectrogram that Figure 10 is embodiment 2 gained catalyzer.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, and unrestricted the present invention.
A kind of method that provides solution method to prepare graphene-based nonmetal oxygen reduction catalyst of invention can comprise the following steps:
Step 1: according to Hummer ' s(Hummers, W.S.& Offeman, R.E.PREPARATION OF GRAPHITIC OXIDE.Journal of the American Chemical Society80,1339-1339 (1958)) method prepares graphene oxide;
Step 2: for example, at certain temperature (70～120 ℃), graphene oxide is added in wide-necked bottle to make concentration be preferably 0.5～1mg/ml of 0.1～5mg/ml() graphene oxide solution, and magnetic agitation (stirring velocity can be 0～1000rpm, preferably, behind 300～500rpm1～3 hour, then add reductive agent;
Above-mentioned graphene oxide can be the graphite oxide (referring to Fig. 1 and Fig. 2) of individual layer or minority basic unit, and graphite oxide or Graphene are the brown color flaky substance, are of a size of 100～1000nm.
Graphene oxide solution solvent used can be organic solvent or inorganic solvent, as water, ethanol and other dispersion agent.
The reductive agent of reductive agent used for containing nonmetallic heteroatoms (N, S, B and/or I), such as sodium sulphite, sodium borohydride, sodium bisulfite, ammonium sulfide, hydrazine hydrate, hydroiodic acid HI etc.
The preparation method of graphene-based non-metallic catalyst provided by the invention is simple, cost is low, and whole process step in solution (preferred aqueous solutions) completes, without too high temperature.This preparation method is at elements such as N, S that Graphene reduction process situ is adulterated, without extra nitrogenous source or the sulphur source of adding.
Originally the catalyzer made has that the hydrogen reduction performance is good, the excellent properties such as have extended cycle life, hydrogen reduction catalytic performance and stability are preferably especially arranged under acidity or alkaline condition: by Fig. 5 and Fig. 7, can find out that the 0.45V left and right has obvious hydrogen reduction peak, illustrates that the catalyzer prepared has the hydrogen reduction performance; By Fig. 6 and Fig. 8, can be found out, through 1000 circulations, the peak strength at hydrogen reduction peak and peak position do not occur significantly to change, can prove that the catalyzer hydrogen reduction obtained has good stability, by Fig. 9 and Figure 10, can find that element sulphur is by being doped in catalyzer of success, doping content is 1.2mol% and 2.5mol%.
Further set forth the present invention below in conjunction with specific embodiment.But, should be understood that these embodiment only do not form limitation of the scope of the invention for the present invention is described.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all per-cent and umber are by mol.
Embodiment 1:
According to Hummer ' s(Hummers, W.S.& Offeman, R.E.PREPARATION OF GRAPHITIC OXIDE.Journal of the American Chemical Society80,1339-1339 (1958)) method prepares graphene oxide and is made into the solution that concentration is approximately 0.8mg/ml.Get above-mentioned solution 10ml and put into wide-necked bottle, wide-necked bottle is placed in to water-bath and uses magnetic stirring apparatus vigorous stirring, temperature to remain on 90 ℃.Dropwise add the sodium sulfide solution 50ml that concentration is 20mg/ml after 2h, and continue to stir 24h at 90 ℃.By above-mentioned solution centrifugal, washing, drying, obtain catalyzer.This catalyzer is sheet (referring to Fig. 3), contains element sulphur, and the content of element sulphur is 2.5mol%.The 0.45V left and right has obvious hydrogen reduction peak as seen from Figure 5, illustrates that the catalyzer prepared has the hydrogen reduction performance; As seen from Figure 6, through 1000 circulations, the peak strength at hydrogen reduction peak and peak position do not occur significantly to change, can prove that the catalyzer hydrogen reduction obtained has good stability, pass through Fig. 9, can find that element sulphur is by being doped in catalyzer of success, doping content is 1.2mol% and 2.5mol%.
According to hummer ' s(Hummers, W.S.& Offeman, R.E.PREPARATION OF GRAPHITIC OXIDE.Journal of the American Chemical Society80,1339-1339 (1958)) method prepares graphene oxide and is made into the solution that concentration is approximately 0.8mg/ml.Get above-mentioned solution 10ml and put into wide-necked bottle, wide-necked bottle is placed in to water-bath, temperature remains on 90 ℃.Dropwise add the sodium sulfide solution 50ml that concentration is 50mg/ml after 2h, and continue to stir 24h at 90 ℃.By above-mentioned solution centrifugal, washing, drying, obtain catalyzer.This catalyzer is block (referring to Fig. 4), contains element sulphur, and the content of element sulphur is 1.2mol%.The 0.45V left and right has obvious hydrogen reduction peak as seen from Figure 7, illustrates that the catalyzer prepared has the hydrogen reduction performance; As seen from Figure 8, through 1000 circulations, the peak strength at hydrogen reduction peak and peak position do not occur significantly to change, can prove that the catalyzer hydrogen reduction obtained has good stability, by Figure 10, can find that element sulphur is by being doped in catalyzer of success, doping content is 1.2mol%.
According to hummer ' s(Hummers, W.S.& Offeman, R.E.PREPARATION OF GRAPHITIC OXIDE.Journal of the American Chemical Society80,1339-1339 (1958)) method prepares graphene oxide and is made into the solution that concentration is approximately 0.8mg/ml.Get above-mentioned solution 10ml and put into wide-necked bottle, wide-necked bottle is placed in to water-bath and uses magnetic stirring apparatus vigorous stirring, temperature to remain on 70 ℃.The ammonium sulfide solution 20ml that dropwise adds 45wt% after 2h, and continue to stir 24h at 70 ℃.By above-mentioned solution centrifugal, washing, drying, obtain catalyzer.This catalyzer is sheet, contains element sulphur and nitrogen element, and the content of element sulphur is 1.5mol%, and the content of nitrogen element is 2.1mol%
According to hummer ' s(Hummers, W.S.& Offeman, R.E.PREPARATION OF GRAPHITIC OXIDE.Journal of the American Chemical Society80,1339-1339 (1958)) method prepares graphene oxide and is made into the solution that concentration is approximately 0.8mg/ml.Get above-mentioned solution 10ml and put into wide-necked bottle, wide-necked bottle is placed in to water-bath, temperature remains on 90 ℃.Dropwise add 45wt% ammonium sulfide solution 50ml after 2h, and continue at 90 ℃ of insulation 24h.By above-mentioned solution centrifugal, washing, drying, obtain catalyzer.This catalyzer is block, and the content that contains element sulphur and nitrogen elementary sulfur element is 1mol%, and the content of nitrogen element is 2mol%.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (8)
1. a method for preparing graphene-based nonmetal oxygen reduction catalyst, it is characterized in that, the graphene-based oxygen reduction catalyst that described graphene-based nonmetal oxygen reduction catalyst is the nonmetallic heteroatoms doping, described nonmetallic heteroatoms comprises N, S, B and/or I, described method comprises:
It is 0.1～5 mg/ml graphene oxide solution that graphene oxide is mixed with to concentration;
Under 70～120 ℃, described graphene oxide solution is stirred after 1～3 hour and is added the reductive agent that contains described nonmetallic heteroatoms, keep 70～120 ℃ continue to stir 18～48 hours so that when redox graphene in-situ doped described nonmetallic heteroatoms; And centrifugal, washing and dry gained solid make described graphene-based nonmetal oxygen reduction catalyst.
2. method according to claim 1, is characterized in that, described reductive agent is at least one being selected from sodium sulphite, sodium borohydride, sodium bisulfite, ammonium sulfide, hydrazine hydrate and hydroiodic acid HI.
3. method according to claim 1, is characterized in that, described nonmetallic heteroatoms is S, and described reductive agent is sodium sulphite and/or sodium pyrosulfate.
4. method according to claim 1, is characterized in that, described nonmetallic heteroatoms is S and N, and described reductive agent is ammonium sulfide.
5. according to the described method of any one in claim 1～4, it is characterized in that, the mol ratio of described graphene oxide and reductive agent is 1:(0.05～0.2).
6. according to the described method of any one in claim 1～4, it is characterized in that, the concentration of described graphene oxide solution is 0.5～1mg/ml.
7. according to the described method of any one in claim 1～6, it is characterized in that, prepared according to Hummer ' s method by described graphene oxide.
8. according to the described method of any one in claim 1～7, it is characterized in that, the solvent for use of described graphene oxide solution is water and/or ethanol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106115667A (en) * | 2016-06-20 | 2016-11-16 | 南京工程学院 | The low temperature preparation method of S, N codope Graphene and application |
| CN106395801A (en) * | 2016-08-30 | 2017-02-15 | 北京化工大学 | Methods for preparing N-doped graphene and N-doped graphene/metal oxide nano composite material at low temperature |
| CN106602064A (en) * | 2016-12-27 | 2017-04-26 | 深圳市川马电子股份有限公司 | Preparation method and application of iodine-doped graphene |
| CN109560293A (en) * | 2018-11-01 | 2019-04-02 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and its preparation method and application |
| CN111285357A (en) * | 2018-12-10 | 2020-06-16 | 河南工程学院 | Method for preparing iodine-nitrogen double-doped graphene based on one-step hydrothermal method |
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| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
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| CN103145122A (en) * | 2013-03-25 | 2013-06-12 | 西北工业大学 | Preparation method of nitrogen-doped graphene |
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| CN101987729A (en) * | 2010-11-08 | 2011-03-23 | 中国科学技术大学 | Method for preparing graphene by reduction of sulfur-contained compound |
| KR20130022565A (en) * | 2011-08-25 | 2013-03-07 | 한국과학기술원 | Nitrogen-doped graphene, ultracapacitor using the same and doping methode of the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106115667A (en) * | 2016-06-20 | 2016-11-16 | 南京工程学院 | The low temperature preparation method of S, N codope Graphene and application |
| CN106395801A (en) * | 2016-08-30 | 2017-02-15 | 北京化工大学 | Methods for preparing N-doped graphene and N-doped graphene/metal oxide nano composite material at low temperature |
| CN106395801B (en) * | 2016-08-30 | 2018-07-24 | 北京化工大学 | A kind of method of low temperature preparation nitrogen-doped graphene and nitrogen-doped graphene/metal oxide nano composite material |
| CN106602064A (en) * | 2016-12-27 | 2017-04-26 | 深圳市川马电子股份有限公司 | Preparation method and application of iodine-doped graphene |
| CN109560293A (en) * | 2018-11-01 | 2019-04-02 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and its preparation method and application |
| WO2020087990A1 (en) * | 2018-11-01 | 2020-05-07 | 江苏可兰素汽车环保科技有限公司 | Oxygen reduction catalyst and preparation method therefor and use thereof |
| CN111285357A (en) * | 2018-12-10 | 2020-06-16 | 河南工程学院 | Method for preparing iodine-nitrogen double-doped graphene based on one-step hydrothermal method |
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Application publication date: 20131211 |