CN108249421A - A kind of method that three-dimensional class graphene structural carbon material is prepared using catalyst - Google Patents

A kind of method that three-dimensional class graphene structural carbon material is prepared using catalyst Download PDF

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Publication number
CN108249421A
CN108249421A CN201810205652.7A CN201810205652A CN108249421A CN 108249421 A CN108249421 A CN 108249421A CN 201810205652 A CN201810205652 A CN 201810205652A CN 108249421 A CN108249421 A CN 108249421A
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China
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product
carbon material
prepared
sample
washed
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Inventor
殷立雄
张�浩
张峰
程如亮
张浩繁
房佳萌
蔺英
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Priority to CN201810205652.7A priority Critical patent/CN108249421A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

A kind of method that three-dimensional class graphene structural carbon material is prepared using catalyst：Pure ethyl cellulose and NaOH formation aaerosol solutions soluble in water will be analyzed, suspension will be transferred in polytetrafluoroethylene (PTFE) water heating kettle later, 80~120 DEG C of reaction 12h in homogeneous reactor.Then products therefrom is centrifuged, and is washed respectively three times using deionized water and absolute ethyl alcohol, 70 DEG C of dryings are for 24 hours in an oven by prepared product later.Weigh the product and Ni (COO) of 2g preparations2It is 100 in mass ratio:5~20 ratio is uniformly mixed.By mixture under an argon atmosphere in 700~1000 DEG C of 1~3h of carbonization treatment, carbonized product is washed with deionized, filter, is dried, obtains carbonized product.Carbonized product in 20% HCl solution is impregnated into 48h, removes remaining Ni simple substance in sample.Sample will be prepared later to be filtered, washed, and until pH value of solution=6.5~7.2, will prepare sample after 60 DEG C are dried processing 12h, you can obtain the product with three-dimensional class graphene-structured.

Description

A kind of method that three-dimensional class graphene structural carbon material is prepared using catalyst
Technical field
The present invention relates to a kind of preparation methods of three-dimensional class graphene structural carbon material, and in particular to a kind of to use catalyst The method that catalysis prepares three-dimensional class graphene structural carbon material.
Background technology
Graphene is carbon atom with sp2The chip architecture that hydridization is formed, because it is with big specific surface area, good electric conductivity Can, good physical and chemical stability, high light transmission rate and high mechanical strength, since the pass for being found just to cause people Note.Equipment needed for graphene preparation is complicated, and manufacturing cost is high, its large-scale application is caused to be restricted.Three-dimensional graphite-like structure Carbon material has a physicochemical properties of similar graphene, at the same its with three-dimensional net structure lead to it with big ratio table Area, big interlamellar spacing, while its preparation process is simple, equipment requirement is low, and production cost is low, is expected to become stone in certain fields The substitute products of black alkene, and large-scale application.
The three-dimensional class graphene carbon material of preparation reported at present method primary template-CVD method [Zongping Chen, Wencai Ren, Libo Gao, Bilu Liu, Songfeng Pei and Hui-Ming Cheng, Three- dimensional flexible and conductive interconnected graphene networks grown by Chemical vapour deposition [J], Nature Materials, 10,424-428 (2011)], graphene oxide from Construction from part [Yuxi Xu, Zhaoyang Lin, Flexible Solid-State Supercapacitors Based on Three Dimensional Graphene Hydrogel Films [J] .ACS NANO, 5,4042-4049 (2013], biology Carbon synthetic method [Xiang-Fen Jiang, Xue-Bin Wang, High-throughput fabrication of strutted graphene by ammonium-assisted chemical blowing for high-performance supercapacitors[J],Nano energy,2015,16:81-90] wherein template-CVD method need to sacrifice template, using first The non-renewable resources such as alkane are raw materials for production, cause production cost high, low yield.Graphene oxide self-assembly method need to prepare oxidation Graphene is predecessor, and complex process, production cost is high, is unfavorable for mass producing.
Invention content
It is low, simple for process and easy to operate the purpose of the present invention is to provide a kind of equipment requirement, low energy consumption, easily control The method that three-dimensional class graphene structural carbon material is prepared using catalyst of system.
In order to achieve the above object, the preparation method that the present invention uses is as follows：
1) by analytically pure ethyl cellulose and NaOH with 1：1~3 molar ratio formation aaerosol solution soluble in water, later Suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle, 80~120 DEG C of reaction 12h obtain product A in homogeneous reactor；
2) by product A and Ni (COO)2By 100:5~20 mass ratio is uniformly mixed to obtain mixture；
3) by mixture under an argon atmosphere in 700~1000 DEG C of 1~3h of carbonization treatment, by carbonized product deionized water Washing filters, is dry, obtains carbonized product；
4) carbonized product is placed in impregnate in HCl solution and obtains sample to remove remaining Ni simple substance in sample；
5) sample filtered, washed, until pH value of solution=6.5~7.2 have three-dimensional after 60 DEG C of drying to obtain Class graphene structural carbon material.
The ethyl cellulose is the ethyl cellulose after hydro-thermal method is handled.
The mass concentration of the HCl is 20%.
The present invention prepares the carbon materials with three-dimensional class graphene-structured using ethyl cellulose as raw material, using nickel acetate catalysis Material, reaction raw materials are easy to get and at low cost, and technological feasibility is strong, prepare that equipment needed for sample is simple, and low energy consumption, using water as reacting Solvent, safety is good, and feasibility is strong, and prepared three-dimensional class graphene carbon material has preferable charge storage performance, simultaneously Production cost is greatly reduced, is had broad application prospects.
Description of the drawings
Fig. 1 is the Raman spectrogram of three-dimensional class graphene-structured product prepared by the embodiment of the present invention 1.
It is scanning electron microscope (SEM) figure that the embodiment of the present invention 1 prepares three-dimensional class graphene-structured product that Fig. 2, which is,.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1：
It 1) will be through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with 1：1 molar ratio formation soluble in water Suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle by aaerosol solution later, and 100 DEG C of reaction 12h must be produced in homogeneous reactor Object A；
2) by product A and Ni (COO)2By 100：5 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 800 DEG C of carbonization treatment 3h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=7.0 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.
As shown in Figure 1, sample manufactured in the present embodiment is in 1372cm-1、1693cm-1And 2763cm-1There is carbon material in place Characteristic peak, while 2763cm-1The 2D peaks for locating the carbon material occurred show that prepared carbon material has similar to graphene Structure.
As shown in Figure 2, the microscopic appearance of sample manufactured in the present embodiment is about 8nm for thickness, and length is 100-300nm's The three-dimensional network-like structure that laminated structure is assembled into.With reference to above analysis shows having prepared the class with three-dimensional net structure Graphene structural carbon material.
Embodiment 2：
It 1) will be through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with 1：2 molar ratio formation soluble in water Suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle by aaerosol solution later, and 110 DEG C of reaction 12h must be produced in homogeneous reactor Object A；
2) by product A and Ni (COO)2By 100：10 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 900 DEG C of carbonization treatment 2h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=6.8 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.
Embodiment 3：
1) by through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with 2 molar ratio it is soluble in water formed it is outstanding Suspension, is transferred in polytetrafluoroethylene (PTFE) water heating kettle by floating solution later, and 120 DEG C of reaction 12h obtain product in homogeneous reactor A；
2) by product A and Ni (COO)2By 100：15 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 1000 DEG C of carbonization treatment 3h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=6.6 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.
Embodiment 4：
1) by through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with the formation soluble in water of 11 molar ratio Suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle by aaerosol solution later, and 80 DEG C of reaction 12h obtain product in homogeneous reactor A；
2) by product A and Ni (COO)2By 100：20 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 700 DEG C of carbonization treatment 1h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=7.1 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.
Embodiment 5：
It 1) will be through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with 1：1.5 molar ratio shape soluble in water Into aaerosol solution, suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle later, 90 DEG C of reaction 12h must be produced in homogeneous reactor Object A；
2) by product A and Ni (COO)2By 100：8 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 850 DEG C of carbonization treatment 2.5h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=6.5 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.
Embodiment 6：
It 1) will be through hydro-thermal method treated analytically pure ethyl cellulose and NaOH with 1：2.5 molar ratio shape soluble in water Into aaerosol solution, suspension is transferred in polytetrafluoroethylene (PTFE) water heating kettle later, 105 DEG C of reaction 12h are obtained in homogeneous reactor Product A；
2) by product A and Ni (COO)2By 100：12 mass ratio is uniformly mixed to obtain mixture；
3) carbonized product is washed with deionized, taken out under an argon atmosphere in 950 DEG C of carbonization treatment 1.5h by mixture Filter, drying, obtain carbonized product；
4) carbonized product is placed in the HCl solution that mass concentration is 20% and impregnates 48h to remove remaining Ni in sample Simple substance obtains sample；
5) sample filtered, washed, until pH value of solution=7.2 have three-dimensional class graphite after 60 DEG C of drying to obtain Alkene structure carbon material.

Claims (3)

  1. A kind of 1. method that three-dimensional class graphene structural carbon material is prepared using catalyst, it is characterised in that including following step Suddenly：
    1) by analytically pure ethyl cellulose and NaOH with 1：1~3 molar ratio formation aaerosol solution soluble in water, later will be outstanding Supernatant liquid is transferred in polytetrafluoroethylene (PTFE) water heating kettle, and 80~120 DEG C of reaction 12h obtain product A in homogeneous reactor；
    2) by product A and Ni (COO)2By 100:5~20 mass ratio is uniformly mixed to obtain mixture；
    3) carbonized product is washed with deionized water under an argon atmosphere in 700~1000 DEG C of 1~3h of carbonization treatment for mixture It washs, filter, dry, obtain carbonized product；
    4) carbonized product is placed in impregnate in HCl solution and obtains sample to remove remaining Ni simple substance in sample；
    5) sample filtered, washed, until pH value of solution=6.5~7.2 have three-dimensional class stone after 60 DEG C of drying to obtain Black alkene structure carbon material.
  2. 2. the method according to claim 1 that three-dimensional class graphene structural carbon material is prepared using catalyst, special Sign is：The ethyl cellulose is the ethyl cellulose after hydro-thermal method is handled.
  3. 3. the method according to claim 1 that three-dimensional class graphene structural carbon material is prepared using catalyst, special Sign is：The mass concentration of the HCl is 20%.
CN201810205652.7A 2018-03-13 2018-03-13 A kind of method that three-dimensional class graphene structural carbon material is prepared using catalyst Pending CN108249421A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332677A (en) * 2013-07-12 2013-10-02 天津工业大学 Method for preparing biomass carbon-based composite energy storage material by utilizing plant fiber
CN104649246A (en) * 2013-11-18 2015-05-27 湖南师范大学 Low temperature hydrothermal preparation method of biomass carbon microsphere / nanosphere
CN105060289A (en) * 2015-09-21 2015-11-18 中南大学 Method for preparing fewer-layer graphene on basis of biomass waste
CN106467298A (en) * 2016-05-04 2017-03-01 济南圣泉集团股份有限公司 A kind of grapheme material and preparation method thereof
CN107369563A (en) * 2016-05-12 2017-11-21 复旦大学 A kind of preparation method of nickel sulphide particles/cellulose base composite carbon aerogel material
US9896342B1 (en) * 2017-09-27 2018-02-20 King Saud University Synthesis of nanostructures from Phoenix dactylifera agro-wastes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332677A (en) * 2013-07-12 2013-10-02 天津工业大学 Method for preparing biomass carbon-based composite energy storage material by utilizing plant fiber
CN104649246A (en) * 2013-11-18 2015-05-27 湖南师范大学 Low temperature hydrothermal preparation method of biomass carbon microsphere / nanosphere
CN105060289A (en) * 2015-09-21 2015-11-18 中南大学 Method for preparing fewer-layer graphene on basis of biomass waste
CN106467298A (en) * 2016-05-04 2017-03-01 济南圣泉集团股份有限公司 A kind of grapheme material and preparation method thereof
CN107369563A (en) * 2016-05-12 2017-11-21 复旦大学 A kind of preparation method of nickel sulphide particles/cellulose base composite carbon aerogel material
US9896342B1 (en) * 2017-09-27 2018-02-20 King Saud University Synthesis of nanostructures from Phoenix dactylifera agro-wastes

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Title
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QIONG WU ET AL: "Ni-doped mesoporous carbon obtained from hydrothermal carbonization of cellulose and their catalytic hydrogenation activity study", 《J.MATER.SCI》 *

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