CN103663438B - A kind of preparation method of porous graphene - Google Patents
A kind of preparation method of porous graphene Download PDFInfo
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- CN103663438B CN103663438B CN201310582747.8A CN201310582747A CN103663438B CN 103663438 B CN103663438 B CN 103663438B CN 201310582747 A CN201310582747 A CN 201310582747A CN 103663438 B CN103663438 B CN 103663438B
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Abstract
The preparation method of a kind of porous graphene provided by the invention, comprises the following steps: the preparation of porous oxidation Graphene: by graphite oxide solution ultrasonic disperse, obtain graphene oxide solution; Centrifugal, obtain colloidal precipitation; Colloidal precipitation is mixed with strong acid, ultrasonic reaction, be washed to pH4-6, lyophilize, obtain porous oxidation Graphene; The preparation of porous graphene: reductive agent and porous oxidation Graphene react, and obtain porous graphene.The method adopts strong acid corrosion and ultrasonication to combine, make the porous graphene aperture that obtains homogeneous, and can adjust in tens nanometers ~ a few micrometer range as required, pore size distribution range is large, the method technique is simple, preparation efficiency is high, with low cost, be suitable for large-scale commercial production.
Description
Technical field
The invention belongs to material engineering field, particularly a kind of preparation method of Graphene derived material porous graphene.
Background technology
Graphene is found in 2004 by the An Deliehaimu of Univ Manchester UK etc., and this material is subject to scientific circles immediately and pays close attention to widely after announcing.Graphene is the monolayer carbon atom of the cellular crystalline network of two-dimentional six side of tightly packed one-tenth, is the thinnest known material at present.The special six side's honeycomb structures of Graphene have contained the abundant and physical phenomenon of novelty, and it not only has excellent electric property that (under room temperature, electronic mobility can reach 2 × 10
5cm
2v
-1s
-1), outstanding heat conductivility (5000Wm
-1k
-1), the specific surface area (2630m of superelevation
2g
-1), its Young's modulus (1100GPa) and breaking tenacity (125GPa) also can match in excellence or beauty with nanotube simultaneously.In addition, the physical properties of the uniqueness that it also has, as perfect quantum tunneling effect, half-integer quantum hall effect and the specific conductivity etc. that never disappears.Graphene can be predicted be with a wide range of applications in the nano electron device and unicircuit, flexible electronic device, ultra-high sensitive sensor Novel electronic devices, matrix material, solar cell, super capacitor and hydrogen storage material etc. in future.
The Van der Waals force high due to graphene film interlayer and very strong π-π reactive force, cause it in preparation process, even if without External Force Acting, is also easy to reunite, thus its surface-area can not be made full use of; Therefore its surface is spilt cruelly for giving full play to grapheme material performance particularly important.Porous graphene is exactly the hole with nano-scale by the method manufacture of physics or chemistry in the lamella of Graphene, thus the effective defects such as solution Graphene is reunited, surface-area can not make full use of, give full play to the advantage of this two-dimensional nano sheet layer material, effectively improve material and the mobility of energy in grapheme material; Therefore, porous graphene is preferably as the energy, catalysis or sorbing material, thus significantly improves the performance of various application porous graphene material devices.
Preparation at present about porous graphene rarely has report, only method all adopts potassium hydroxide under high temperature and inert atmosphere, to carry out chemical activation to Graphene and obtains porous graphene, the method complex process, obtained porous graphene pore diameter range is very little, only can prepare the porous graphene that aperture is 0.5 ~ 5nm, seriously limit the subsequent applications of this novel graphite alkene derived material.
Summary of the invention
Goal of the invention: the object of the present invention is to provide that pore diameter range is large, controllable and the preparation method of homogeneous porous graphene.
Technical scheme: the preparation method of a kind of porous graphene provided by the invention, comprises the following steps:
(1) preparation of porous oxidation Graphene: by graphite oxide solution ultrasonic disperse, obtain graphene oxide solution; Centrifugal, obtain colloidal precipitation; Colloidal precipitation is mixed with strong acid, ultrasonic reaction, be washed to pH4-6, obtain porous oxidation Graphene;
(2) preparation of porous graphene: reductive agent and porous oxidation Graphene react, and obtain porous graphene.
In step (1), the concentration of described graphite oxide solution is 0.01-20g/L.
In step (1), centrifugal speed is 5000 ~ 20000rpm.
In step (1), described strong acid to be massfraction be 65 ~ 70% nitric acid or massfraction be the hydrofluoric acid of 40 ~ 47%; The amount ratio of graphite oxide and strong acid is (0.1-5) g:1L.
In step (1), ultrasonic disperse frequency is 20 ~ 80kHz; The ultrasonic disperse time is 30 ~ 180min.
In step (1), ultrasonic reaction frequency is 15-100kHz; The ultrasonic reaction time is 30-240min.
In step (2), described reductive agent is hydrazine hydrate, a hydrazine hydrate, sodium borohydride or xitix.
In step (2), the mass ratio (0.5 ~ 20) of reductive agent and porous oxidation Graphene: 1.
In step (2), temperature of reaction is 50-100 DEG C, and the reaction times is 10min-24h.
In step (2), react and carry out in water solvent, the amount ratio of porous oxidation Graphene and water is (0.01-20) g:1L.
Beneficial effect: the inventive method adopts strong acid corrosion and ultrasonication to combine, make the porous graphene aperture that obtains homogeneous, and can adjust in tens nanometers ~ several micrometer range as required, pore size distribution range is large, the method technique is simple, preparation efficiency is high, with low cost, be suitable for large-scale commercial production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the graphite oxide that the present invention uses.
Fig. 2 is the scanning electron microscope (SEM) photograph of the porous graphene that the present invention obtains.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
1) preparation of porous oxidation Graphene:
Get 0.02g graphite oxide, be mixed with the solution that 100ml concentration is 0.2g/L, ultrasonic 30min under 20kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 10000rpm, collect bottom GO colloid, be the salpeter solution mixing of 70% with 200ml mass concentration by GO colloid, ultrasonic 30min under 15kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 4, and lyophilize obtains the porous oxidation Graphene solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 0.01g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 1L, getting 0.05g sodium borohydride joins in graphene oxide solution, 6h is reacted at temperature is 100 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.
Fig. 2 is the scanning electron microscope (SEM) photograph of obtained porous oxidation Graphene, and clearly can find out that from figure the surface of Graphene has nano level hole to occur, size is at about 50nm.
Embodiment 2
1) preparation of porous oxidation Graphene:
Get 0.015g graphite oxide, be mixed with the solution that 1.5L concentration is 0.01g/L, ultrasonic 60min under 40kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 12000rpm, collect bottom GO colloid, be the hydrofluoric acid solution mixing of 40% with 15ml mass concentration by GO colloid, ultrasonic 60min under 28kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 5, and lyophilize obtains the graphene oxide solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 0.5g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 20ml, getting 0.2g xitix joins in graphene oxide solution, 10min is reacted at temperature is 80 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.The bore hole size of obtained porous graphene is at about 70nm.
Embodiment 3
1) preparation of porous oxidation Graphene:
Get 0.3g graphite oxide, be mixed with the solution that 60ml concentration is 5g/L, ultrasonic 100min under 50kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 15000rpm, collect bottom GO colloid, be the salpeter solution mixing of 68% with 150ml mass concentration by GO colloid, ultrasonic 120min under 60kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 6, and lyophilize obtains the graphene oxide solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 5g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 50ml, the 15ml hydrazine hydrate aqueous solution got containing 0.25g hydrazine hydrate joins in graphene oxide solution, 10h is reacted at temperature is 50 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.The bore hole size of obtained porous graphene is at about 100nm.
Embodiment 4
1) preparation of porous oxidation Graphene:
Get 0.5g graphite oxide, be mixed with the solution that 50ml concentration is 10g/L, ultrasonic 150min under 70kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 20000rpm, collect bottom GO colloid, be the salpeter solution mixing of 65% with 125ml mass concentration by GO colloid, ultrasonic 200min under 80kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 6, and lyophilize obtains the graphene oxide solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 10g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 50ml, the 10ml hydrazine hydrate aqueous solution got containing 0.25g hydrazine hydrate joins in graphene oxide solution, 24h is reacted at temperature is 80 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.The bore hole size of obtained porous graphene is at about 100nm.
Embodiment 5
1) preparation of porous oxidation Graphene:
Get 0.5g graphite oxide, be mixed with the solution that 25ml concentration is 20g/L, ultrasonic 180min under 80kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 5000rpm, collect bottom GO colloid, be the hydrofluoric acid solution mixing of 47% with 100ml mass concentration by GO colloid, ultrasonic 240min under 100kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 6, and lyophilize obtains the graphene oxide solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 20g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 10ml, 20ml mono-hydrazine hydrate aqueous solution got containing 0.2g mono-hydrazine hydrate joins in graphene oxide solution, 16h is reacted at temperature is 70 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.The bore hole size of obtained porous graphene is at about 300nm.
Embodiment 5
Embodiment 6
1) preparation of porous oxidation Graphene:
Get 0.1g graphite oxide, be mixed with the solution that 100ml concentration is 1g/L, ultrasonic 180min under 60kHz frequency, obtain graphene oxide (GO) solution.Then solution is centrifugal under 10000rpm, collect bottom GO colloid, be the hydrofluoric acid solution mixing of 47% with 500ml mass concentration by GO colloid, ultrasonic 240min under 40kHz frequency, then deionized water is added, centrifuge washing repeatedly under same rotating speed, system being washed till pH is 6, and lyophilize obtains the graphene oxide solid with nano aperture.
2) preparation of porous graphene:
Be the solution of 10g/L by the mass concentration that the porous oxidation Graphene solid obtained in step 1 is mixed with 10ml, 10ml mono-hydrazine hydrate aqueous solution got containing 0.1g mono-hydrazine hydrate joins in graphene oxide solution, 16h is reacted at temperature is 70 DEG C, obtain the graphene dispersing solution of porous, filtration washing, lyophilize obtains the porous graphene solid with nano aperture.The bore hole size of obtained porous graphene is at about 3 μm.
In sum, the present invention innovatively by graphene oxide colloidal dispersion in concentrated acid solution, under ultrasound condition, utilize the corrodibility of strong acid and the chemically reactive of graphene oxide, at surface of graphene oxide corrosion pore-forming, and by regulation and control strong acid and the ratio of graphene oxide and the time of ultrasonic reaction, prepare the Graphene of different pore size scope, meet the application requiring of porous graphene in different field.This preparation method is simple simultaneously, raw material is easy to get, cost is low, efficiency is high, be applicable to industrialization scale operation.
Claims (1)
1. a preparation method for porous graphene, is characterized in that: comprise the following steps:
(1) preparation of porous oxidation Graphene: by graphite oxide solution ultrasonic disperse, obtain graphene oxide solution; Centrifugal, obtain colloidal precipitation; Colloidal precipitation is mixed with strong acid, ultrasonic reaction, be washed to pH4-6, obtain porous oxidation Graphene; Described strong acid to be massfraction be 40 ~ 47% hydrofluoric acid; The amount ratio of graphite oxide and strong acid is (0.1-5) g:1L; The concentration of described graphite oxide solution is 0.01-20g/L; Centrifugal speed is 5000 ~ 20000rpm; Ultrasonic disperse frequency is 20 ~ 80kHz; The ultrasonic disperse time is 30 ~ 180min; Ultrasonic reaction frequency is 15-100kHz; The ultrasonic reaction time is 30-240min;
(2) preparation of porous graphene: reductive agent and porous oxidation Graphene react, and obtain porous graphene; Wherein, described reductive agent is hydrazine hydrate, a hydrazine hydrate, sodium borohydride or xitix; The mass ratio (0.5 ~ 20) of reductive agent and porous oxidation Graphene: 1; Temperature of reaction is 50-100 DEG C, and the reaction times is 10min-24h; Reaction is carried out in water solvent, and the amount ratio of porous oxidation Graphene and water is (0.01-20) g:1L.
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| CN104194234B (en) * | 2014-08-14 | 2017-06-06 | 济南圣泉集团股份有限公司 | A kind of Graphene glass steel board composite and preparation method thereof |
| WO2016191564A1 (en) * | 2015-05-26 | 2016-12-01 | The Regents Of The University Of California | Dispersions of holey graphene materials and applications thereof |
| US10160653B2 (en) * | 2016-05-31 | 2018-12-25 | City University Of Hong Kong | Method of producing graphene-based materials, obtainable materials and their use |
| CN106315563B (en) * | 2016-07-27 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of grapheme material of ordered structure and preparation method thereof |
| CN106241784B (en) * | 2016-07-27 | 2019-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the grapheme material of multilevel structure |
| CN106556677B (en) * | 2016-10-27 | 2018-07-06 | 苏州大学 | A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof |
| CN108622880B (en) * | 2017-03-15 | 2021-05-18 | 国家纳米科学中心 | Reduced graphene peroxide, interlayer material containing same and lithium-sulfur battery |
| CN107324318A (en) * | 2017-07-10 | 2017-11-07 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | The method of the preparation of porous graphene and manganese oxide porous graphene composite |
| CN110117001A (en) * | 2018-02-06 | 2019-08-13 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
| CN108163845B (en) * | 2018-03-21 | 2020-12-22 | 绍兴市梓昂新材料有限公司 | Preparation method of porous graphene material |
| CN108675683A (en) * | 2018-06-22 | 2018-10-19 | 苏州市贝克生物科技有限公司 | Graphene oxide is composite porous |
| CN109324096A (en) * | 2018-09-27 | 2019-02-12 | 台州学院 | A kind of preparation method of graphene enhancing sensor |
| CN110400930A (en) * | 2019-08-15 | 2019-11-01 | 马鞍山科达普锐能源科技有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN115057437B (en) * | 2022-05-30 | 2023-11-24 | 苏州大学 | SnO (tin oxide) 2 NiO/graphene ternary composite material and preparation method and application thereof |
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| CN102935233A (en) * | 2012-11-05 | 2013-02-20 | 中国科学院长春应用化学研究所 | Phospholipid membrane-graphene composite material and preparation method thereof |
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| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103050704A (en) * | 2012-12-28 | 2013-04-17 | 清华大学深圳研究生院 | Porous conductive additive and preparation method thereof, lithium ion battery |
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