CN104211058A - Method for preparing graphene from conducting polymer polyaniline - Google Patents
Method for preparing graphene from conducting polymer polyaniline Download PDFInfo
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- CN104211058A CN104211058A CN201410486824.4A CN201410486824A CN104211058A CN 104211058 A CN104211058 A CN 104211058A CN 201410486824 A CN201410486824 A CN 201410486824A CN 104211058 A CN104211058 A CN 104211058A
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- polyaniline
- graphene
- carbonization
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Abstract
The invention relates to a method for preparing graphene from conducting polymer polyaniline. The method includes mixing a certain amount of iron-based catalysts with the polyaniline, inspecting the influence of calcining temperatures on polyaniline carbonization for preparation of the graphene, and analyzing structural changes and morphologies of the graphene through an X-ray diffraction spectrum, a Raman spectrum, a high resolution electron microscope. In application, the method includes carbonizing the polyaniline under the temperature ranging from 1000 DEG C to 1600 DEG C and then adding an appropriate amount of iron catalysts into the carbonized polyaniline so as to achieve low-temperature carbonization preparation of the graphene through the polyaniline. According to the method for preparing the graphene from the conducting polymer polyaniline, the polyaniline or wastes of the polyaniline are used as a carbon source, iron simple substance, iron oxide, carbonyl iron, ferroferric oxide and the like are used as catalysts, a reaction is performed in a high temperature furnace in the presence of high-purity nitrogen, and the carbonization temperature ranges from 1000 DEG C to 1600 DEG C.
Description
Technical field
The present invention relates to conductive polymer polyanaline carbonization at low temperature legal system for Graphene.
Background technology
Greying be by the charcoal of densification at high temperature (2400 DEG C-2800 DEG C) heat-treat, make charcoal make the impurity element effusions such as N, H, O, K, Na, Ca wherein at a certain temperature, charcoal is transformed into the process of the crystal structure of graphite of three-dimensional order by turbostratic.Carbon can be realized by the conversion of decolorizing carbon to graphite through high temperature cabonization process.And Graphene a kind of forms hexagonal honeycomb lattice flat film by carbon atom sp2 hybridized orbital, be a kind of graphite of individual layer sheet.Graphite is carried out stripping by physics or chemical process and can obtain Graphene, from Geim in 2004 successfully adopt micromechanics stripping method from level to level from graphite, separate Graphene since (Science, 2004, 306 (5696): 666-669), preparation method's research both at home and abroad about Graphene has a lot of report: the people such as Berger prepare individual layer and multi-layer graphene by heating SiC, this method is harsh to environmental requirement, must High Temperature High Pressure and the Graphene prepared is not easily separated is difficult to scale operation (Science, 2006, 312:1191-1196), Kim etc. use the silicon chip of polycrystalline Ni film as matrix, chemical Vapor deposition process is utilized to prepare large-area graphene, the standby Graphene specific conductivity of this legal system is high, transparency is high, can be used for preparing electronic component, but complex process and cost intensive etc. constrain the development (Nature, 2009,457 (7230): 706-710) that vapour deposition process prepares Graphene, Recent study the most widely method is that oxidation reduction process prepares Graphene, patent of invention and research paper report are a lot, mainly first prepare graphene oxide by 3 kinds of classical Standenmaier methods, Brodie method, Hummers method, again graphene oxide is reduced into Graphene by chemistry or heat treating method, or direct is raw material with graphene oxide, prepare the Graphene with different components and structure by chemical treatment.And be carbon source with carbon material, the report being prepared Graphene by high temperature cabonization is also few.Zhong Chunyans etc. take biology cellulose as raw material, through dehydration, high-temperature calcination 1-4 hour under the oxygen-free environment of 600-1200 DEG C, use strong oxidizer to carry out graded oxidation in different thermogrades to the biology cellulose after anaerobic calcining more under strongly acidic conditions, finally carry out reduction reaction with reductive agent again and obtain grapheme material (CN 103332684A); Chen Wei etc. with the amine small molecules of the carbohydrate molecule of carbon containing and carbon containing nitrogen for mixture material, under argon atmosphere, by the grapheme material (CN103274393A) of N doping obtained after 700-1000 DEG C of calcining; Zhou Mingjie etc. with organic carbon source and organic nitrogen source be mixed with suspension at the bottom of high temperature-resistant liner on, the grapheme material (CN102887501A) of the obtained N doping of reaction at 500-1300 DEG C, and be raw material with polyaniline, the research preparing Graphene by high temperature sintering in the presence of a catalyst is also not yet reported.
Polyaniline is as a kind of conducting polymer composite, have a wide range of applications in senser element, pH measurement, gas detection, ray detection, infrared optical device, along with increasing gradually of polyaniline consumption, its corresponding waste also becomes the important topic that polymer reclaims, because its special molecular structure makes it there is certain difficulty in solvability, partial solvent is only had to dissolve polyaniline.This research, for the application market of existing polyaniline, by polyaniline or its waste method by carbonization at low temperature, is realized by the conversion of polyaniline to Graphene by this body structure changing material.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art, take polymer polyanilinc as carbon source, and with metallic iron simple substance and compound thereof for catalyzer, the carbonization at low temperature realizing this polymer materials under the condition of 1600 DEG C prepares Graphene.The inventive method is simple to operate, and temperature of reaction is low, is beneficial to suitability for industrialized production.
The object of the invention is to propose novel method prepared by a kind of Graphene.
Another object of the present invention is to take polyaniline as carbon source, Graphene is prepared in the carbonization realizing material by adding suitable catalyzer, finds the new opplication field of polyaniline.
The present invention is realized by following manner:
Described macromolecular material is polyaniline or its waste; Described catalyzer is iron powder, ferric oxide, iron carbonyl, metal molysite etc., and catalyst particle size is micron order.
Embodiment of the present invention are:
Take polyaniline as carbon source, Metallic iron and iron--containing compounds is catalyzer, and reaction process is carried out under high pure nitrogen atmosphere in tube furnace.Polyaniline is incubated 1.5 hours at 400 DEG C and carries out carbonizing treatment, the particle of particle diameter at about 75um is obtained with 200 mesh sieve screenings, preset temperature (1000-1600 DEG C) is warming up to again after being mixed with the Fe-series catalyst of certain content by particle, be incubated 4 hours, obtained decolorizing carbon and Graphene blend, blend is used respectively the vitriol oil/potassium permanganate solution of certain proportioning, concentrated hydrochloric acid solution reflow treatment, required grapheme material can be obtained.
The present invention not only as the low-temperature catalyzed graphitization fundamental research of polyaniline, can the more important thing is as obtaining the novel method preparing grapheme material.
Accompanying drawing explanation
The X-ray diffraction spectrogram of Fig. 1 differing temps carbonization polyaniline.
The laser Raman spectroscopy figure of Fig. 2 differing temps carbonization polyaniline.
The high-resolution electron microscope figure of Figure 31 000 DEG C of carbonization polyaniline.
X-ray diffraction (XRD) collection of illustrative plates measures (Cu target, Ka radiation, λ=0.15406nm) by Beijing Pu Xi universal apparatus company limited XD-3 type X-ray diffraction analysis instrument, operating voltage 36kV, tube current 30mA, sweep limit 10-80 °, sweep velocity is 3 °/min.Laser raman analysis adopts Horiva (LabRam HR-800) Raman spectroscopy, laser source wavelength 514nm, power 25mW, Raman shift range: 800-2000cm-1.Transmission electron microscope photo (TEM) is obtained by company of Jeol Ltd. JEOL-2010 type transmission electron microscope.
Embodiment
Embodiment:
With polyaniline or its waste for raw material, ferric oxide is catalyzer, wherein catalyst quality content is 10% of monomer mass, polyaniline is warming up to 400 DEG C with 5 DEG C/min, insulation 1.5h, obtains the powder particle of particle diameter at about 75um with 200 mesh sieve screenings, is warming up to preset temperature (1000-1600 DEG C) again after the Fe-series catalyst of powder particle and certain content is even by mechanically mixing, be incubated 4 hours, obtained decolorizing carbon and Graphene mixture.Mixture is put into the vitriol oil/potassium permanganate mixing solutions (H
2o/H
2sO
4/ KMnO
4=1:0.02:0.006) middle backflow 2h, suction filtration, also with obtaining brownish black pressed powder after deionized water wash, obtaining black solid after filtration after pressed powder dissolves with excessive concentrated hydrochloric acid, deionized water wash, being Sheet Graphite alkene.
Gained sample shows (Fig. 1) through X-ray diffraction analysis: under catalyst oxidation iron exists, along with temperature is elevated to 1600 DEG C from 1000 DEG C, (002), (101) diffraction peak change after polyaniline carbonization is little, corresponding (002), (101) diffraction angle is respectively 26.50 ° and 45.30 °, simultaneously (100) diffraction peak of graphite is also high-visible after polyaniline carbonization as we can see from the figure, shows that polyaniline changes the carbon structure of polyaniline under having catalyzer to exist after 1000-1600 DEG C of carbonization.
Gained sample obtains Fig. 2 through Raman analysis.There are 9 kinds of lattice vibrations in graphite-structure, the vibration of two E2g types is wherein had to have Raman active, a Raman bands (called after D bands of a spectrum) is wherein obtained at 1360cm-1 place, this is due to imperfect crystal introducing, this spectral line is called structural disorder peak, its intensity reflects be the situation of crystalline texture disorder; And be single crystal graphite institute peculiar (called after G bands of a spectrum) at the frequency band at 1580cm-1 place, be the stretching vibration of C-C key in graphite lattice plane, be used for characterizing the integrated degree of sp2 hybrid bond structure in graphite-structure.This just shows in Raman collection of illustrative plates, there is certain corresponding relation between the relative intensity at 1360cm-1 and 1580cm-1 place and material degree of graphitization.Integrated intensity ratio (the R=I at conventional two peaks traditionally
1360/ I
1580) carry out the quality of evaluating graphite degree.Fig. 2 shows the Raman spectrogram of polyaniline in differing temps carbonization, as can be seen from figure we, along with carbonization temperature is increased to 1600 DEG C from 1000 DEG C, carbon structure order degree after polyaniline carbonization increases gradually, the intensity at corresponding D bands of a spectrum and G bands of a spectrum peak increases gradually, and simultaneously under 1600 DEG C of hot conditionss, the intensity of G bands of a spectrum diffraction peak is larger, the carbon structure ordering degree of polyaniline is better, corresponding R value (R=I
d/ I
g) being reduced to 0.426 from 1.350, display is orderly carbon structure preferably.
Fig. 3 is the high-resolution electronic Photomicrograph of resin 1000 DEG C of carbonizations, and the transparent sheet structure of Graphene is in reuniting or overlapping state as seen from the figure, high-visible, and display iron p-poly-phenyl amine has good catalyzed graphitization effect.
Claims (10)
1. the method for Graphene is prepared in polyaniline carbonization, it is characterized in that: polyaniline is added appropriate catalyzer and carry out carbonization at 1000-1600 DEG C and prepare Graphene.
2. the method for Graphene is prepared in polyaniline carbonization according to claim 1, it is characterized in that: by polyaniline carbonization 1.5 hours at 400 DEG C, obtain the carbon material preparing Graphene.
3. method according to claim 2, it is characterized in that: carbonization method obtains by controlling heating schedule, its heating schedule is: within 1.5 hours, carried out in 80 DEG C of insulations, 1 hour, 280 DEG C insulations, 1 hour, 400 DEG C insulations successively by polyaniline, after sample carbonization, porphyrize is also crossed 200 mesh sieve and obtained the polyaniline powder of particle diameter at about 75um.
4. the method for Graphene is prepared in polyaniline carbonization according to claim 1, it is characterized in that: by described Fe-series catalyst and polyaniline powder blended 1 hour at normal temperatures, and blend method adopts mechanical stirring, obtains dispersed system.
5. method according to claim 4, it is characterized in that: described catalyzer/polyaniline carbonized powder mixture is warming up to 400 DEG C with 5 DEG C/min, be warming up to carbonization temperature with the temperature rise rate of 2 DEG C/min after insulation 2h, obtain Graphene and decolorizing carbon mixture.
6. method according to claim 5, is characterized in that: carbonization temperature is 1000-1600 DEG C.
7. method according to claim 5, it is characterized in that: by the decolorizing carbon that obtains after carbonization and Graphene mixture through water/vitriol oil/potassium permanganate mixed-liquor return 2h, by products therefrom through suction filtration, deionized water repeated washing, until neutrality, obtains Manganse Dioxide and Graphene mixture.
8. method according to claim 7, is characterized in that: the ratio of the amount of substance of the water/vitriol oil/potassium permanganate is H
2o/H
2sO
4/ KMnO
4=1:0.02:0.006, wherein water is deionized water, and sulfuric acid mass content is 98%, and potassium permanganate is analytical reagent.
9. method according to claim 7, is characterized in that: by Manganse Dioxide and Graphene mixture through concentrated hydrochloric acid dissolution process, after suction filtration with deionized water repeated washing to neutral, obtain black patch layer graphene.
10. method according to claim 9, is characterized in that: the mass content of concentrated hydrochloric acid used is 36.5%.
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| CN103342357A (en) * | 2013-07-16 | 2013-10-09 | 安徽理工大学 | Low temperature catalytic graphitization method for polydivinylbenzene resin |
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| CN105885780A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Preparation method of nano-composite mesoporous material |
| CN104830271A (en) * | 2015-01-12 | 2015-08-12 | 刘艳娇 | Preparation method of thermoelectric thin film |
| CN104830275A (en) * | 2015-01-12 | 2015-08-12 | 刘艳娇 | Thermoelectric thin film |
| CN105879846A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Nano-composite mesoporous material |
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| CN104531062A (en) * | 2015-01-12 | 2015-04-22 | 冯丹 | Method for preparing nano-composite wave absorbing material |
| WO2017063492A1 (en) * | 2015-10-15 | 2017-04-20 | 济南圣泉集团股份有限公司 | Composite containing carbon nanostructure, high molecular material using same and preparation method |
| KR20170063550A (en) * | 2015-10-15 | 2017-06-08 | 지난 셩취엔 그룹 쉐어 홀딩 코., 엘티디. | Composite having carbon nanostructure, macromolecular material using the same and processes for preparing the same |
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