CN102153073B - Self-assembly preparation method and application of solid/liquid interface of graphene oxide hydrogel - Google Patents
Self-assembly preparation method and application of solid/liquid interface of graphene oxide hydrogel Download PDFInfo
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Abstract
The invention discloses a self-assembly preparation method and application of a solid/liquid interface of graphene oxide hydrogel. The method comprises the following steps of: preparing graphite oxide powder and deionized water into a solution with the concentration of 1-7 mg/mL; and immersing a porous anodic alumina film or an aluminum sheet, an aluminum foil or a copper sheet treated by a mixed liquid of concentrated sulfuric acid and hydrogen peroxide in a water solution of graphene oxide at 0-80 DEG C to form graphene oxide hydrogel on the surface of the porous anodic alumina film, the aluminum sheet, the aluminum foil or the copper sheet. The graphene oxide hydrogel is used for preparing graphene oxide aerogel and graphene aerogel and is also a coating of the graphene oxide hydrogel. The preparation method provided by the invention is simple and does not require any high-temperature high-pressure process, and the water mass of the graphene oxide hydrogel is more than 99%.
Description
Technical field
The present invention relates to a kind of solid-liquid interface self-assembly preparation method thereof and application of graphene oxide hydrogel, belong to graphene oxide hydrogel technology.
Background technology
Graphene is just receiving widely with its excellent electronic transmission performance, thermal property, mechanical property etc. and paying close attention to; And graphene oxide is as the Graphene precursor; More owned special performances; Though it is unlike the extensive concern of the such belongings neo-confucian of Graphene, the parent who has but obtained chemists looks at.Multiple oxygen-containing functional group on graphene oxide basal plane and the edge is given its higher chemically reactive, and wherein carboxyl mainly is distributed on the edge of graphene oxide, and hydroxyl and epoxide group mainly are distributed on the basal plane.The graphene oxide negatively charged ion that partial ionization produced of carboxyl makes and can form the stable graphene oxide water-sol with the electrostatic interaction of mutual repulsion between its lamella on its edge.The foreign study personnel find that graphene oxide can regard a kind of amphipathic flexible molecule as, because the conjugated six-membered carbon ring is given its hydrophobic nature, abundant oxygen-containing functional group makes it have certain wetting ability.Because the amphipathic character of graphene oxide, make that it can stable existence [Franklin Kim, Laura J.Cote, JiaxingHuang on the liquid-liquid interface of organic solvent and aqueous solution formation; Advanced Materials, 2010,22,1954-1958]; Can disperse powdered graphite and carbon nanotube [Jaemyung Kim, Laura J.Cote, Jiaxing Huang through the solid/liquid interfaces self-assembly; Journal of theAmerican Chemical Society, 2010,132; 8180-8186], can also form graphene oxide film [Cheng-Meng Chen, Quan-Hong Yang through the liquid-gas interface self-assembly; Et al.AdvancedMaterials, 2009,21; 3007-3011], the graphene film that the graphene oxide film that makes obtains through reduction can be used as good thermally conductive material, and on the transparent counter electrode of solar cell, also has great application potential.In a word, the interface is that the self-assembly of graphene oxide provides ideal platform to remove to construct the functional materials of various ways.Yet; Interface self-assembly research for graphene oxide at present mainly concentrates on gas/liquid interface and liquid/liquid interface; Also great majority also just are directed against microcosmic graphene oxide lamella in solid/liquid interfaces self-assembly research, and very few in the research that the solid/liquid interfaces self-assembly forms the function nano nacrostructure for graphene oxide.
Hydrogel by the assembling of graphene oxide lamella has eco-friendly characteristics, can be applied in drug delivery and the bioengineered tissue, also has great application potential in fields such as catalysis, absorption and electrochemical energy storages.People such as Shi reported through hydrothermal method and carried out graphene oxide hydrogel [Yuxi Xu, Gaoquan Shi, the et al.ACS Nano that self-assembly forms partial reduction; 2010; 4324-4330], this gel has mechanical property and chemical property preferably, but the process that obtains this hydrogel relates to HTHP; Though HTHP can amplify, be undoubtedly a kind of very operation of power consumption in industry.
Summary of the invention
The object of the present invention is to provide a kind of solid-liquid interface self-assembly preparation method thereof and application of graphene oxide hydrogel.This procedure is simple; Do not need power consumption processes such as HTHP, the graphene oxide hydrogel that makes has the character of general hydrogel, and water cut is more than 99%; Have mechanical property preferably, can be used as the coating of graphene oxide and be used for the gas gel of oxygenerating Graphene.
The present invention realizes that through following technical scheme a kind of solid-liquid interface self-assembly preparation method thereof of graphene oxide hydrogel is characterized in that comprising following process:
With graphite oxide powder and deionized water according to mass ratio 7: the 7-1 ratio adds in the beaker, is that 120～300W carries out ultrasonic concussion 2～10h with ultrasonic power, obtains finely disseminated graphite oxide aqueous solution.
2. be aluminium flake, aluminium foil or the copper sheet of 98% vitriol oil and ydrogen peroxide 50 mixed solution processing in 3: 1 by volume with porous anodic alumina film or use massfraction; The concentration that is immersed in step 1 system is in 1～7mg/mL graphite oxide aqueous solution; Under 0～80 ℃ of temperature, soak 4～168h, on the surface of porous anodic alumina film, aluminium flake, aluminium foil or copper sheet, then form the graphene oxide hydrogel.
With the application of the graphene oxide hydrogel of method for preparing, be to carry out lyophilize 24～48h under-57～-61 ℃ with the graphene oxide hydrogel that makes at condenser temperature, obtain the graphene oxide gas gel; In argon gas atmosphere, is 200～700 ℃ under to carry out thermal reduction handle 2～10h in temperature to this graphene oxide gas gel, obtains the Graphene gas gel; In addition, the graphene oxide hydrogel also is a kind of coating of graphene oxide.
The invention has the advantages that; The graphene oxide hydrogel that makes according to present method has the character of general gel, and the preparation method is simple and convenient, need not relate to the process of any HTHP; Hydrogel contains quality more than 99%; Be suitable as coating and be coated on the various matrixes, and the shape of this gel is easy to fix, have mechanical property preferably.Also can handle through freeze-drying and obtain corresponding graphene oxide gas gel, this aerogel material has the microcosmic vesicular structure, has bigger application prospect aspect absorption and the catalysis.Thermal treatment reduction and chemical reduction to the graphene oxide gas gel can obtain the Graphene gas gel again, and the Graphene gas gel has good electrochemical energy storage performance.
Description of drawings
Fig. 1 is embodiment 1 a prepared graphene oxide hydrogel photo in kind.
Fig. 2 is the thermogravimetric curve of embodiment 1 prepared graphene oxide hydrogel.
Fig. 3 is embodiment 7 prepared graphene oxide gas gels photos in kind.
Fig. 4 is embodiment 8 prepared Graphene gas gels photos in kind.
Embodiment
Embodiment 1
With two classical step anode oxidation methods aluminium foil is carried out electrochemical oxidation and handle, obtain the porous anodic alumina film of pore size distribution at 10-200nm.Detailed process be with aluminium foil successively in acetone and alcohol solvent sonic oscillation clean 10min, then with the soaking with sodium hydroxide of 1mol/L to remove surperficial natural oxide layer.Then in perchloric acid and ethanol volume ratio are 1: 1 solution, carry out electrochemical etching, voltage is set to 12V, is mirror-smooth until the surface.Under the room temperature condition; In the sulfuric acid electrolyte of 0.3～1.2mol/L, voltage is under 15～25V, with the bigger aluminium flake of another area as counter electrode; Carry out anodize one time, using massfraction then is 1.8% chromic acid and 6.0% phosphoric acid mixed liquid dipping membrane removal.Carry out the anodic oxidation second time again, secondary oxidizing condition is with for the first time identical.Be under 8～15V condition at voltage at last,, utilize the effect of liberation of hydrogen bubbling that porous anodic alumina film is come off from the aluminium foil matrix the power positive cathode exchange.
Prepare the graphite oxide powder with improving the Hummers method.10g powdered graphite and 5g SODIUMNITRATE are being mixed under agitation condition with the vitriol oil of 230mL 98% under the ice-water bath condition; Then 30g potassium permanganate is slowly joined in this mixed solution; The temperature of maintenance mixed solution continues to stir 2hr under 1 ℃, afterwards mixed solution being transferred to bath temperature is 35 ℃ of continuation stirring 30min down.Deionized water with 460mL joins in this mixed solution lentamente then; Add temperature that the speed of zero(ppm) water controls mixed solution below 100 ℃ through control; At last bath temperature is brought up to 98 ℃; Under this temperature, continue to stir 3hr, dilute resulting glassy yellow product with deionized water afterwards, and clean with the ydrogen peroxide 50 of 30mL30% to increase the degree of oxidation of graphite; Then eccentric cleaning is till the pH of scavenging solution value becomes neutrality repeatedly, and just product carries out vacuum-drying 48hr and obtains the graphite oxide powder at last.
This graphite oxide powder of 80mg is dispersed in the 80mL deionized water, uses the cell pulverization appearance under 120W power, the graphite oxide powder to be carried out strong supersound process 2h and obtain concentration and be the finely dispersed graphite oxide aqueous solution of 1mg/mL.
Porous anodic alumina film with above-mentioned preparation is inserted in this graphite oxide aqueous solution then, at room temperature leaves standstill 4h, just can obtain 40cm
3Graphene oxide hydrogel (as shown in Figure 1), this graphene oxide hydrogel can bear the upset test, and it contains quality (as shown in Figure 2) more than 99%.
Embodiment 2
Present embodiment is identical with embodiment 1 process, just changes the add-on of graphite oxide: become 560mg by 80mg.The constancy of volume of the graphene oxide hydrogel that obtains, just the water cut of hydrogel has lacked 0.1%.
Embodiment 3
Present embodiment is identical with embodiment 1 process, just changes ultrasonic power: become 300W by 120W.This process has just changed graphene oxide lamella size in the graphite oxide aqueous solution, and the volume and the water cut of the graphene oxide hydrogel that obtains are constant.
Embodiment 4
Present embodiment is identical with embodiment 1 process, just changes ultrasonic time: become 10h by 2h.This process has just changed graphene oxide lamella size in the graphite oxide aqueous solution, and the graphene oxide hydrogel volume and the water cut that obtain are constant.
Embodiment 5
Present embodiment is identical with embodiment 1 process, just changes the insertion time of porous anodic alumina film: become 168h by 4h.The hydrogel water cut that makes is lower.
Embodiment 6
Present embodiment is identical with embodiment 1 process, just changes to be inserted into the MOX in the graphite oxide aqueous solution: becoming the use volume ratio by porous anodic alumina film is 3: 1 the vitriol oil and 1 * 5cm of each 5min of ydrogen peroxide 50 mixed solution 40mL oxide treatment
2Copper sheet obtains the copper sheet that the surface has thin oxide layer.Obtain the about 30cm of volume
3The graphene oxide hydrogel, its water cut is still more than 99%.
Embodiment 7
The graphene oxide hydrogel that embodiment 1 is obtained is packed in the 5mL plastics centrifugal bottle; It is immersed in 10min makes the rapid cryofixation of hydrogel in the liquid nitrogen; Sample after will fixing then is positioned in the FD-1-50 type Freeze Drying Equipment; At condenser temperature is-57 ℃, and pressure is under the condition of 6Pa, carries out lyophilize processing 24h and just can obtain graphene oxide gas gel (as shown in Figure 3).
Embodiment 8
Embodiment 7 resulting graphene oxide gas gels in argon gas atmosphere, through 200 ℃ of thermal treatment 2h, are obtained Graphene gas gel (as shown in Figure 4).
Embodiment 9
Present embodiment is identical with embodiment 8 processes, just changes thermal treatment temp: become 700 ℃ by 200 ℃.The Graphene gas gel oxygen-containing functional group that obtains lacks than the Graphene gas gel oxygen-containing functional group that embodiment 8 makes.
Claims (1)
1. the solid-liquid interface self-assembly preparation method thereof of a graphene oxide hydrogel is characterized in that comprising following process:
1) with graphite oxide powder and deionized water according to mass ratio 7: the 7-1 ratio adds in the plastic beaker, is that 120～300W carries out ultrasonic concussion 2～10h with ultrasonic power, obtains finely disseminated graphite oxide aqueous solution;
2) be the aluminium foil or the copper sheet of 98% vitriol oil and ydrogen peroxide 50 mixed solution processing in 3: 1 by volume with porous anodic alumina film or use massfraction; The concentration of the step 1) system of being immersed in is in 1～7mg/mL graphite oxide aqueous solution; Under 0～80 ℃ of temperature, soak 4～168h, on the surface of porous anodic alumina film, aluminium foil or copper sheet, then form the graphene oxide hydrogel.
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| TW201326036A (en) * | 2011-12-27 | 2013-07-01 | Ind Tech Res Inst | Methods of forming graphene |
| CN102701188B (en) * | 2012-05-07 | 2014-11-12 | 华中科技大学 | Method for preparing three-dimensional porous graphene material by solution |
| CN103606662B (en) * | 2013-11-12 | 2017-01-11 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based tin dioxide composite material |
| CN104157884B (en) * | 2014-07-30 | 2016-10-05 | 华南理工大学 | Three-diemsnional electrode brush that a kind of 3D graphene oxide aeroge is modified and preparation method and application |
| CN104495820A (en) * | 2014-12-17 | 2015-04-08 | 北京化工大学 | Porous graphene aerogel and preparation method thereof |
| CN104607052B (en) * | 2015-01-13 | 2016-09-28 | 山东应天节能环保科技有限公司 | A kind of alkalescence low-phosphorous reverse osmosis membrane antisludging agent and preparation method |
| CN105648428B (en) * | 2015-12-28 | 2018-04-10 | 东莞市义仁汽车租赁有限公司 | A kind of lightweight heat dissipation film of sandwich structure and preparation method thereof |
| CN105647249B (en) * | 2016-03-16 | 2017-12-26 | 浙江大学 | A kind of method of ion induction assembling graphite ene coatings |
| CN105645400B (en) * | 2016-03-16 | 2018-12-04 | 浙江大学 | A kind of graphene self-supporting material and preparation method thereof of ion induction assembling |
| CN106629678A (en) * | 2016-12-12 | 2017-05-10 | 天津师范大学 | Method for preparing multi-element co-doped graphene by hydrothermal method |
| CN110010883A (en) * | 2019-04-03 | 2019-07-12 | 山东星火科学技术研究院 | A kind of high efficiency aluminium-sulfur battery negative electrode material and synthesis technology that graphene is modified |
| CN112141174B (en) * | 2020-09-21 | 2023-01-20 | 通号城市轨道交通技术有限公司 | ZC simulation system and method in VOBC test environment |
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| CN101654245A (en) * | 2009-10-10 | 2010-02-24 | 天津大学 | Solid-liquid interface self-assembly preparation method for graphene oxide film |
| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
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| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
| CN101654245A (en) * | 2009-10-10 | 2010-02-24 | 天津大学 | Solid-liquid interface self-assembly preparation method for graphene oxide film |
| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
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Application publication date: 20110817 Assignee: Inner Mongolia Rising New Energy Co., Ltd. Assignor: Tianjin University Contract record no.: 2013990000201 Denomination of invention: Self-assembly preparation method and application of solid/liquid interface of graphene oxide hydrogel Granted publication date: 20121114 License type: Exclusive License Record date: 20130507 |
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