CN102886276A - Preparation method of Co/graphene-PAN (polyacrylonitrile) composite material - Google Patents
Preparation method of Co/graphene-PAN (polyacrylonitrile) composite material Download PDFInfo
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- CN102886276A CN102886276A CN2012103855290A CN201210385529A CN102886276A CN 102886276 A CN102886276 A CN 102886276A CN 2012103855290 A CN2012103855290 A CN 2012103855290A CN 201210385529 A CN201210385529 A CN 201210385529A CN 102886276 A CN102886276 A CN 102886276A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a preparation method of Co/graphene-PAN (polyacrylonitrile) composite material. The method comprises the following steps of: 1, preparing graphene/PAN and keeping graphene/PAN wet; 2, preparing Co/graphene, drying Co/graphene and then wetting Co/graphene with distilled water; adding the products obtained in the steps 1 and 2 into distilled water, stirring and carrying out heat preservation; 4, washing the fiber product with distilled water and drying the fiber product at a low temperature to finally obtain the Co/graphene-PAN (polyacrylonitrile) composite material. The prepared Co/graphene-PAN composite material has the advantages that Co particles are uniformly distributed on the surface of PAN; and the speed of hydrogen production by using sodium borohydride catalyzed with the Co/graphene-PAN composite material is about three times as high as the speed of hydrogen production by using sodium borohydride catalyzed with Co/graphene, so the Co/graphene-PAN composite material has a broad application prospect.
Description
Technical field
The invention belongs to graphene-based composite manufacture field, particularly a kind of preparation method of polyacrylonitrile fibre Supported Co/graphene composite material.
Background technology
Graphene be a kind of by carbon atom by sp
2Carbon lattice close-packed arrays forms the stratified material that is similar to alveolate texture, is subject in recent years the extensive concern of scientific circles.The electronic movement velocity of Graphene reaches 1/300 of the light velocity, that is to say considerably beyond the movement velocity of electronics in general conductor, and many research expectations are by compound to reach the purpose that improves the material electrical property with Graphene.In addition, Graphene also has a lot of good performances: good heat-conductive characteristic, mechanical performance, chemical stability, large surface area-to-volume ratio, this is so that it has huge application prospect at many sciemtifec and technical spheres such as nanoelectronics, sensor, nano composite material, battery, ultracapacitor and hydrogen storages.
Recent study person finds that graphene composite material can significantly improve the performances such as raw-material electrical conductivity, thermal conductivity, mechanical strength, catalytic performance.Shi etc. have reported by simple flask reaction supported by cobalt oxide is surperficial to Graphene at J Harzard Mater.229 – 230 (2012) 331 – 339, obtained removing the cobalt oxide/graphene composite material of water oxygen azo dyes.This catalyst material catalytic efficiency is high, good stability, and preparation is simple, for it provides reliable basis in application aspect the sewage disposal.Liu etc. have reported by electrochemical reducing in Journal of Power Sources 195 (2010) 4628-4633 and have prepared Pt/ expansible graphite alkene nanometer sheet, the Pt uniform particles that diameter is about 15nm is dispersed in the graphene layer, improved the electrocatalysis characteristic of graphene nanometer sheet, good stability.Gao etc. have reported take urea as fuel that in Carbon 50 (2012) 4093 – 4101 alkali formula Titanium Nitrate is oxidant, have prepared Graphene/titanium oxide composite material by a step firing method.Wherein there is a certain amount of N atom on the graphene film, compare with the Graphene/titanium oxide composite material that does not have the N atom, this material is under illumination, light induced electron and hole more are difficult for compound, also can find out from the experiment of degraded methyl orange, its redox ability effectively strengthens, and also provides a new thinking for preparing other graphene-based catalyst.
Only pay close attention to the research of granular composite material preparation and property about the research major part of graphene composite material.And the specific area of Graphene own is very large, reunites easily, and in Nano-composite materials, agglomeration traits is more outstanding.The present invention loads to organic synthetic fibers with graphene nanocomposite material--the polyacrylonitrile fibre material surface, and study its catalytic performance, its meaning is: (1) loads on fiber surface with graphene-based nano composite material, can effectively improve the dispersiveness of composite in liquid reaction system, reach the purpose that improves material property; (2) fiber is one-dimensional material, and has pliability, is applied to easily in the difform reactor; (3) fiber-like catalyst is easy to reclaim more, effectively reduces catalyst loss; (4) character such as organic synthetic fibers length, thickness, whiteness, gloss can be regulated in process of production, and have respectively fast light, wear-resisting, easily wash easily the characteristics such as do, do not go rotten, so that the composite range of application is more extensive.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of polyacrylonitrile fibre Supported Co/graphene composite material, and this preparation method is simple, is easy to suitability for industrialized production; Cobalt granule is evenly distributed in polyacrylonitrile fibre (PAN) surface in the prepared graphene coated polyacrylonitrile fibre composite (Co/graphene-PAN), composite has good catalytic performance, and the catalysis sodium borohydride solution prepares hydrogen gas rate than cobalt/graphene composite material (about 900mL
HydrogenMin
-1G
Catalysis Agent -1) improved nearly three times, have broad application prospects.
The preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material of the present invention comprises:
(1) cobalt/graphene composite material Co/graphene and graphene coated polyacrylonitrile fibre composite graphene/PAN preparation;
The preparation of a.Co/graphene
Graphite oxide is scattered in the ethylene glycol solution, behind the ultrasonic dispersion of the gained mixed liquor 60min, add cobalt nitrate, anhydrous sodium acetate and PEG400, stir 2h, form reactant liquor, the proportioning of graphite oxide, ethylene glycol, cobalt nitrate, anhydrous sodium acetate, polyethylene glycol is 55mg:55ml:165mg:1800mg:0.3mL, reactant liquor is at 200 ℃ of lower reaction 12h, reaction finishes, centrifugal collection product, with deionized water, absolute ethanol washing product, then with product dry 12h under 80 ℃, obtain cobalt/graphene composite material.
The preparation of b.graphene/PAN
(1) the NaOH aqueous solution of preparation 14wt% under the room temperature immerses PAN in the NaOH aqueous solution, 110 ℃ of lower insulation 30min, and the deionized water washing is to neutral, and 70 ℃ of lower dry 12h obtain alkali treatment PAN.(2) the KH550 solution of preparation 1mg/mL, wherein solvent is V
Water: V
Absolute ethyl alcoholThe water alcohol mixed liquor of=1:2 soaks 12h with alkali treatment PAN at KH550 solution, and 70 ℃ of lower dry 12h obtain individual layer KH550 modification PAN; (3) the graphite oxide GO dispersion liquid of preparation 1mg/mL under the room temperature places the GO dispersion liquid with KH550 modification PAN, 70 ℃ of lower insulation 3h, and 60 ℃ of lower dry 10h obtain individual layer GO modification PAN; (4) repeating step (2), obtain 3 layers of GO modification PAN for (3) 3 times; (5) 3 layers of GO modification PAN are immersed in the hydrazine hydrate solution of GO dispersion liquid and 50wt%, the volume ratio of GO dispersion liquid and hydrazine hydrate solution is 200:3, be warming up to 100 ℃, reaction 30min, products therefrom is cooled to room temperature, the deionized water washing keeps the gained fibrous composite to be in moisture state to neutral;
(2) with distilled water that dried Co/graphene is wetting;
(3) wetting Co/graphene and graphene/PAN are mixed, mass ratio is 5:1 ~ 7:1, add a certain amount of distilled water after, stir also insulation;
(4) with distilled water washing the fibre product, low temperature drying obtains Co/graphene-PAN.
Cobalt in the described step (3)/Graphene Co/graphene concentration is 0.7 ~ 1.5mg/L.
Graphene coated polyacrylonitrile fibre composite graphene/PAN concentration in the described step (3) is 0.02 ~ 25mg/L.
Stirring means in the described step (3) is mechanical agitation, and holding temperature is 70 ~ 90 ℃, and temperature retention time is 12 ~ 24h.
Baking temperature in the described step (4) is 30 ~ 50 ℃.
Be 6 ~ 12h the drying time in the described step (4).
The present invention aims to provide the preparation method of a kind of effective catalyst polyacrylonitrile fibre Supported Co/graphene composite material Co/graphene-PAN.This method loads on good, the ageing-resistant polyacrylonitrile fibre surface of pliability with the Co/graphene composite, make every effort to solve agglomeration traits and the catalyst recovery problem that Co/graphene occurs in liquid phase reactor, reach the effect that improves material property, enlarges its range of application.And this method process simple, expend littlely, fibrous matrix can change according to actual requirement, the newest research results of combining nano science and technology will improve the actual application value of graphene-based composite greatly.
Beneficial effect
(1) preparation method of the present invention is simple, and is low to the production equipment requirement, is easy to suitability for industrialized production;
(2) cobalt granule is evenly distributed in the PAN surface in the prepared Co/graphene-PAN composite, and composite has good catalytic performance, and the catalysis sodium borohydride solution prepares hydrogen gas rate (3222mL
HydrogenMin
-1G
Catalyst -1) than the about 995mL of Co/graphene(
HydrogenMin
-1G
Catalyst -1) improved nearly three times, have broad application prospects;
(3) prepared Co/graphene-PAN composite can repeatedly use, and it is convenient to reclaim, and easily is applied to difform reactor.
Description of drawings
Fig. 1 is the field emission scanning electron microscope photo (low multiplication factor) of Co/graphene-PAN composite among the embodiment 1;
Fig. 2 is the field emission scanning electron microscope photo (high-amplification-factor) of Co/graphene-PAN composite among the embodiment 1;
Fig. 3 is the speed comparison diagram that Co/graphene-PAN and Co/graphene catalysis sodium borohydride solution prepare hydrogen under embodiment 1 the same terms;
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
(1) preparation 10mg graphene coated polyacrylonitrile fibre composite (graphene/PAN) keeps graphene/PAN to be in moisture state;
The NaOH aqueous solution of preparation 14wt% immerses PAN in the NaOH aqueous solution under a, the room temperature, 110 ℃ of lower insulation 30min, and the deionized water washing is to neutral, and 70 ℃ of lower dry 12h obtain alkali treatment PAN.The KH550 solution of b, preparation 1mg/mL, wherein solvent is V
Water: V
Absolute ethyl alcoholThe water alcohol mixed liquor of=1:2 soaks 12h with alkali treatment PAN at KH550 solution, and 70 ℃ of lower dry 12h obtain individual layer KH550 modification PAN; The graphite oxide GO dispersion liquid of preparation 1mg/mL places the GO dispersion liquid with KH550 modification PAN under c, the room temperature, 70 ℃ of lower insulation 3h, and 60 ℃ of lower dry 10h obtain individual layer GO modification PAN; D, repeating step b, obtain 3 layers of GO modification PAN for c3 time; (5) 3 layers of GO modification PAN are immersed in the hydrazine hydrate solution of GO dispersion liquid and 50wt%, the volume ratio of GO dispersion liquid and hydrazine hydrate solution is 200:3, be warming up to 100 ℃, reaction 30min, products therefrom is cooled to room temperature, the deionized water washing keeps the gained fibrous composite to be in moisture state to neutral;
(2) the dry good Co/graphene of preparation 40mg is measured 20mL distilled water, and is in mortar that Co/graphene is wetting;
Graphite oxide is scattered in the ethylene glycol solution, behind the ultrasonic dispersion of the gained mixed liquor 60min, add cobalt nitrate, anhydrous sodium acetate and PEG400, stir 2h, form reactant liquor, reactant liquor is at 200 ℃ of lower reaction 12h, reaction finishes, and centrifugal collection product is with deionized water, absolute ethanol washing product, then with product dry 12h under 80 ℃, obtain cobalt/graphene composite material.
(3) wetting Co/graphene and graphene/PAN are transferred in the 100mL there-necked flask, add 20mL distilled water after, stir and at 80 ℃ of insulation 12h; (4) with distilled water washing the fibre product, 40 ℃ of lower dry 8h obtain the Co/graphene-PAN composite.Fig. 1 is the field emission scanning electron microscope photo (low multiplication factor) of present embodiment gained composite, Fig. 1 is the field emission scanning electron microscope photo (high-amplification-factor) of present embodiment gained composite, can find out that from the field emission scanning electron microscope photo cobalt granule is dispersed in fiber surface, granular size is 50 ~ 100nm, and open defect does not appear in fiber surface.Fig. 3 is the speed comparison diagram that Co/graphene-PAN and Co/graphene catalysis sodium borohydride solution prepare hydrogen under the same terms, and it is 3222mL that the hydrogen that can find out the Co/graphene-PAN composite produces speed
HydrogenMin
-1G
Catalyst -1, produce speed (about 995mL apparently higher than the hydrogen of Co/graphene composite
HydrogenMin
-1G
Catalyst -1), show excellent catalytic performance.
Embodiment 2
(1) preparation 5mg graphene coated polyacrylonitrile fibre composite (graphene/PAN) keeps graphene/PAN to be in moisture state; (2) take by weighing the dry good Co/graphene of 30mg, measure 15mL distilled water, in mortar that Co/graphene is wetting; (3) wetting Co/graphene and graphene/PAN are transferred in the 100mL there-necked flask, add 25mL distilled water after, stir and at 70 ℃ of insulation 18h; (4) with distilled water washing the fibre product, 50 ℃ of lower dry 6h obtain the Co/graphene-PAN composite.The gained composite prepares in the hydrogen process at the catalysis sodium borohydride aqueous solution, and fiber surface has a large amount of Bubble formations, and hydrogen-producing speed is 3008mL
HydrogenMin
-1G
Catalyst -1
Embodiment 3
(1) preparation 15mg graphene coated polyacrylonitrile fibre composite (graphene/PAN) keeps graphene/PAN to be in moisture state; (2) take by weighing the dry good Co/graphene of 50mg, measure 25mL distilled water, in mortar that Co/graphene is wetting; (3) wetting Co/graphene and graphene/PAN are transferred in the 100mL there-necked flask, add 15mL distilled water after, stir and at 90 ℃ of insulation 24h; (4) with distilled water washing the fibre product, 30 ℃ of lower dry 12h obtain the Co/graphene-PAN composite.The gained composite prepares in the hydrogen process at the catalysis sodium borohydride aqueous solution, and hydrogen-producing speed is 3188mL
HydrogenMin
-1G
Catalyst -1
Embodiment 4
(1) preparation 50mg graphene coated polyacrylonitrile fibre composite (graphene/PAN) keeps graphene/PAN to be in moisture state; (2) take by weighing the dry good Co/graphene of 180mg, measure 50mL distilled water, in mortar that Co/graphene is wetting; (3) wetting Co/graphene and graphene/PAN are transferred in the 250mL there-necked flask, add 110mL distilled water after, stir and at 80 ℃ of insulation 16h; (4) obtain the Co/graphene-PAN composite with 40 ℃ of lower dry 12h of distilled water washing the fibre product.The gained composite prepares in the hydrogen process at the catalysis sodium borohydride aqueous solution, and hydrogen-producing speed is 3016mL
HydrogenMin
-1G
Catalyst -1
Claims (6)
1. the preparation method of a polyacrylonitrile fibre Supported Co/graphene composite material comprises:
(1) preparation graphene coated polyacrylonitrile fibre composite keeps the gained fibrous material to be in moisture state;
(2) preparation cobalt/graphene composite material is wetting with distilled water with dried cobalt/graphene composite material;
(3) wetting cobalt/Graphene and graphene coated polyacrylonitrile fibre composite are mixed, behind the adding distilled water, stir also insulation;
(4) with distilled water washing the fibre product, low temperature drying obtains polyacrylonitrile fibre Supported Co/graphene composite material.
2. the preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material according to claim 1, it is characterized in that: the cobalt in the described step (3)/Graphene concentration is 0.7 ~ 1.5mg/L.
3. the preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material according to claim 1, it is characterized in that: the graphene coated polyacrylonitrile fibre composite concentration in the described step (3) is 0.02 ~ 25mg/L.
4. the preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material according to claim 1, it is characterized in that: the stirring means in the described step (3) is mechanical agitation, and holding temperature is 70 ~ 90 ℃, and temperature retention time is 12 ~ 24h.
5. the preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material according to claim 1, it is characterized in that: the baking temperature in the described step (4) is 30 ~ 50 ℃.
6. the preparation method of a kind of polyacrylonitrile fibre Supported Co/graphene composite material according to claim 1, it is characterized in that: be 6 ~ 12h the drying time in the described step (4).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104372434A (en) * | 2014-11-15 | 2015-02-25 | 辽宁石油化工大学 | Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229425A (en) * | 2011-03-29 | 2011-11-02 | 东华大学 | Method for preparing cobalt/graphene composite material by alcohol thermal method |
| CN102619080A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Preparation method of graphene coating polyacrylonitrile fiber composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229425A (en) * | 2011-03-29 | 2011-11-02 | 东华大学 | Method for preparing cobalt/graphene composite material by alcohol thermal method |
| CN102619080A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Preparation method of graphene coating polyacrylonitrile fiber composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104372434A (en) * | 2014-11-15 | 2015-02-25 | 辽宁石油化工大学 | Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production |
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Application publication date: 20130123 |