CN106006620A - Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel - Google Patents

Graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel Download PDF

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CN106006620A
CN106006620A CN201610361186.2A CN201610361186A CN106006620A CN 106006620 A CN106006620 A CN 106006620A CN 201610361186 A CN201610361186 A CN 201610361186A CN 106006620 A CN106006620 A CN 106006620A
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aeroge
graphene
aerogel
solution
water
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付明来
陈建炜
杨佳诚
苑宝玲
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Institute of Urban Environment of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention relates to graphene oxide aerogel and graphene aerogel, as well as preparation methods and environmental application of graphene oxide aerogel and graphene aerogel. Graphene oxide (GO) aerogel and graphene (G) aerogel are respectively two types of carbon solids which are formed by GO elementary units and G elementary units and adopt a porous and sponge-like structure, and have the characteristics of very low density, very strong hydrophilicity and hydrophobicity, relatively strong elasticity, fire resistance and the like. The aerogel preparation process comprises the following steps: (1) preparation of a graphite oxide precursor, (2) control of graphite oxide properties of functional group type and number, dispersity, concentration, size structure and the like, (3) hydrothermal/solvothermal treatment of a GO (or G) solution, (4) drying (drying and reduction) treatment: after the treatment, GO (or G) aerogel with excellent performance is obtained. The aerogel preparation process is strong in operability and easy to enlarge, and the prepared aerogels have wide application prospects on the aspects of adsorption and removal of dye and waste oil in waste water.

Description

Graphene oxide and graphene aerogel and preparation method thereof and environmental applications
Technical field
The invention belongs to efficient functional material, specifically graphene oxide and graphene aerogel and preparation method thereof and environmental applications, two kinds of aeroges have broad application prospects in fields such as materials chemistry, environment, electronics and the energy.
Background technology
Aeroge (aerogel), is also called xerogel, is to react through chemical solution, forms colloidal sol, then the gel that gelation obtains.Remove the most of solvent in gel, it is thus achieved that a kind of space net structure in gassy, appearance is (close to atmospheric density) porous material that solid, shaped density is extremely low.Aeroge has that density is low, porosity is high, specific surface area is big, thermal conductivity is low and the character such as stable chemical performance, these fundamental propertys can derive other performance, the most heat insulation, sound insulation, shockproof, close/hydrophobic etc..Aeroge is divided into four classes, the first kind is inorganic aerogels (oxide, fluoride, carbide, mixed oxide), Equations of The Second Kind is organic aerogel (aldehyde system, urea derivative, polymer, carbons), 3rd class is gaseous mixture gel (organic+inorganic), and the 4th class is composite aerogel (fibre-reinforced aerogel, other composite aerogel).Common aeroge has silica aerogel, carbon aerogels and aerosil.Graphene oxide and graphene aerogel are the aeroges of latest development, belong to carbon aerogels.
Carbon is one of most common element of distributed in nature, is also to constitute the most important element of all life body on the earth.High-molecular organic material with carbon as main composition, including plastics, rubber and fiber etc., has evolved into one of main subject direction of materialogy three.And with carbon itself, by different structure, combination, a unique Inorganic Non-metallic Materials world can be formed.Can not only be with sp between carbon atom3Hybrid orbital forms singly-bound, moreover it is possible to sp2And sp hybrid orbital forms stable double bond and three key, therefore, in addition to the material with carbon element that nature exists multiple allotrope, scientists has also synthesized numerous structure and the diverse material with carbon element of character by experiment, such as familiar diamond and graphite, and the fullerene with C60 as representative and carbon nanopowder body, tubing, wire rod etc., these carbon nanomaterials are nano material and the emphasis of nano science research all the time.The discovery of nearest Novel Carbon Nanomaterials Graphene and its potential application, promote research and the application of this kind of Novel Carbon Nanomaterials especially.The characteristic of these new carbon almost can contain two kinds of character that the character of all substances on the earth is relatively even vertical, as from the hardest to dead-soft, full extinction-full impregnated light, insulator-quasiconductor-high conductor, thermal insulation-good heat conduction, high ferromagnet, the superconductor etc. of high-critical temperature.Therefore, material with carbon element, as a kind of important material, carries out research and the commercial application of material with carbon element, pays close attention to the Novel Carbon Nanomaterials research based on Graphene, is an important direction of development new high-tech material.
2004, Britain graceful Chester College Physics scholar An Deliehaimu and Constantine's Nuo Woxiao love, from graphite, isolate Graphene (graphene, GR) the most in an experiment, it was demonstrated that Graphene can be with stable existence.Only after 6 years, two people obtain Nobel Prize in physics in 2010 the most jointly.One achievement obtains Nobel Prize from being accomplished to, and was only spaced for 6 years, is the rarest.Graphene is carbon atom two dimension (2D) crystal with sp2 orbital hybridization composition hexagonal honeycomb shape lattice, can be regarded as the base structure of all carbon nanomaterials.Graphene can become the fullerene (fullerence) of zero dimension (0D) with warped；It is curled into the CNT (carbon nanotube, CNT) of one-dimensional (1D) or is stacked into the graphite (graphite) of three-dimensional (3D).Due to Graphene there is the intensity of superelevation and toughness, waterproof, airtight, strong acid-base resistance, can conduct electricity but a series of odd number solution, multiple countries and the research structure such as highly transparent to its Innovation Input great interest.Having scientist even to foretell, Graphene " will thoroughly change 21 century ".
Aeroge is that presoma forms colloidal sol through chemical solution reaction, colloidal sol polymeric gel obtains gel, can be obtained by the most of solvent being dried in (typically supercritical drying and lyophilization) removing colloidal sol and have space net structure gassiness solid aeroge.Graphene oxide and graphene aerogel, with graphite oxide as presoma, obtain graphene oxide colloid solution by ultrasonic disperse, obtain gel through hydrothermal/solvent thermal process, just can obtain aeroge after gel drying.Graphene oxide colloid solution (functional group's kind and quantity, dispersibility and concentration, size, structural intergrity etc.), hydrothermal/solvent thermal process (type of solvent, reaction condition), drying process and subsequent treatment (reduction) etc. are carried out the research of detailed system, it is possible to obtain there is graphene oxide and the graphene aerogel of excellent properties.The application of aeroge is widely, including calorifics field, electricity field, field of acoustics, optical field, filtration and catalytic field, adsorbing domain, fractal property and capture high-velocity particles etc., as a example by calorifics application, aeroge all has in chemical engineering industry, building industry, petroleum industry, transportation industry, crude oil leakage, Aero-Space, national defence, shoes and other civilian industry to be dabbled.The application of graphene oxide and graphene aerogel spreads all trades and professions equally, they have obtained great concern in the application of environmental area, particularly in terms of pollutant Adsorption, the potentiality of environment purification are unlimited, mainly have benefited from their three-dimensional porous structure, structure contains countless macropore, mesopore, mesoporous, micropore, this just gives graphene oxide and the huge specific surface of graphene aerogel, pore volume, add huge pi-conjugated structure, beyond doubt as the optimum selection of adsorbing material.
Summary of the invention
It is an object of the invention to provide graphene oxide and graphene aerogel and preparation method thereof and environmental applications.Graphene oxide (GO) and the carbon solid that Graphene (G) aeroge is that two classes that GO with G elementary cell is constituted have a large amount of hole, similar spongiosis respectively.GO density is 0.3 ~ 2.0 mg/cm3, contact angle 30 ~ 80 °, aperture be 1 nm ~ 5 μm, porosity be 65 ~ 99%, specific surface area be 100 ~ 1700 m2/ g also has relatively strong elasticity and fire line；G density is 0.25 ~ 1.8 mg/cm3, contact angle 95 ~ 150 °, aperture be 1 nm ~ 3.5 μm, porosity be 80 ~ 99%, specific surface area be 300 ~ 2000 m2/ g also has relatively strong elasticity and fire line.
It is a further object of the present invention to provide the controllable method for preparing of described GO and G aeroge, preparation method includes: (1) prepares graphite oxide presoma, (2) graphite oxide character such as functional group's kind and quantity, dispersibility, concentration, dimensional structure etc. are controlled, (3) hot GO(or G of hydrothermal/solvent) solution, (4) after being dried (or being dried and reduction) process, GO(or G that i.e. availability is excellent) aeroge.The purpose of the present invention is realized by techniques below route.
1. the preparation of graphite oxide:
Described graphite oxide solution uses the Hummer method synthesis improved.
(1) 100 ~ 500 mL concentrated sulphuric acids, 1.0 ~ 5.0 g graphite powders and 5.0 ~ 30.0 g potassium permanganate dispersed with stirring 0.5 ~ 3.0 under ice-water bath are taken h。
(2) mixture step (1) obtained keeps 1 ~ 12 h at 25 ~ 50 DEG C.
(3) product obtained toward step (2) adds 100 ~ 300 mL deionized waters, question response system cool 90 ~ 105 DEG C time dropping 2 ~ 10 mL hydrogen peroxide until reaction solution does not has color to change.
(4) by the product of step (3), hydrochloric acid solution and 1500 ~ 7500 mL deionized waters with 250 ~ 1500 mL, volume fraction are 20% ~ 50% carries out washed product successively.
(5) product that previous step obtains being configured to concentration is 0.3 ~ 15 Mg/mL graphite oxide aqueous solution.Gained graphite oxide has abundant oxygen-containing functional group, fragment, and few structure is more complete, size is fabulous at 0.5 ~ 45 μm, dispersibility.
2. the preparation of GO aeroge:
Graphite is after pre-oxidation and performance process, and described GO aeroge is preferably synthesized by solvent thermal and two processes of lyophilization.
(1) taking graphite oxide aqueous solution that 2 ~ 30 mL concentration are 0.3 ~ 15.0 mg/mL and add 0 ~ 118 mL deionized water or ethanol or ethylene glycol, the graphite oxide solution of new preparation is carried out power is 40 ~ 200 W, frequency are 8 ~ 40 KHZ ultrasonic disperse 5 ~ 120 Min obtains GO colloid solution.
(2) the GO colloid solution that step (1) obtains is transferred in inner liner polytetrafluoroethylene reactor, in order to strengthen the mechanical performance of gained graphene oxide aeroge, the high polymer (PEG, PAN and PVDF) of 0.1 ~ 1.0 wt% can be added in a kettle., at 100 ~ 200 DEG C, react 6 ~ 24 h.
(3) being repeatedly washed with deionized 6 ~ 24 times by the GO gel that step (2) obtains, be-5 ~-65 DEG C in cryogenic temperature, vacuum is to be dried 1 ~ 72 h under conditions of 15 ~ 60000 Pa to obtain GO aeroge.
3. the preparation of G aeroge:
Graphite is after pre-oxidation and performance process, and described G aeroge is preferably synthesized by solvent thermal, lyophilization and three processes of reduction treatment.
(1) taking the graphite oxide aqueous solution that 2 ~ 30 mL concentration are 0.3 ~ 15.0 mg/mL, utilize isodensity differential centrifugation that the aqueous solvent of graphite oxide aqueous solution is carried out the displacement of ethanol or ethylene glycol, speed setting is 12000 ~ 18000 Rev/min, graphite oxide aqueous solution adds ethanol every time after being centrifuged first or ethylene glycol carries out high speed centrifugation and to complete ethanol or ethylene glycol, water replaced ethanol or the ethylene glycol solution of preparation graphite oxide 3 ~ 30 times, in order to obtain that there is G aeroge of different nature, graphite oxide ethanol and the mixed liquor of water or ethylene glycol and the mixed liquor of water can be prepared by adding 10 ~ 40 mL deionized waters in the ethanol or ethylene glycol solution of graphite oxide.The new graphite oxide solution prepared is carried out power is 40 ~ 200 W, frequency are 8 ~ 40 KHZ ultrasonic disperse 5 ~ 120 Min obtains GO colloid solution.
(2) the GO colloid solution that step (1) obtains is transferred in inner liner polytetrafluoroethylene reactor, in order to strengthen the mechanical performance of gained G aeroge and improve reducing degree, additive (the 1H of 0.1 ~ 1.0 wt% can be added in a kettle., 1H, 2H, 2H-the most not certain herbaceous plants with big flowers base mercaptan, dopamine, glucose, sucrose etc.).
(3) Graphene (oxide) gel that step (2) obtains is washed with deionized 6 ~ 24 times repeatedly, is-5 ~-65 in cryogenic temperature DEG C, vacuum is to be dried 1 ~ 72 h under conditions of 15 ~ 60000 Pa to obtain Graphene (oxide) aeroge.
(4) Graphene (oxide) aeroge that step (3) obtains being done further reduction treatment, processing method includes under an argon with 300 ~ 1000 DEG C/heating rate of h, 1600 ~ 2800 DEG C high-temperature process 30 ~ 240 min, 40 ~ 80 DEG C 10 ~ 40% hydroiodic acid solution impregnation 3 ~ 24 Under the conditions of 25 ~ 60 DEG C, 12 ~ 48 it are vacuum dried after h H, 40 ~ 80 DEG C 10 ~ 25% ammonia spirit dipping 3 ~ 24 h after be vacuum dried in the sodium borohydride solution of 12 ~ 48 h and 0.5 ~ 5 g/L under the conditions of 25 ~ 60 DEG C and impregnate after 3 ~ 24 h 25 ~ 60 12 ~ 48 h it are vacuum dried under the conditions of DEG C.
Described utilize GO and G aeroge in order to the Adsorption of pollutant in environment.
The present invention compared with prior art has the following advantages。
(1) graphene oxide of the present invention and graphene aerogel have characteristic and the performance of excellence, low-density, high porosity (macropore of countless interconnections, mesopore, mesoporous and micropore), Large ratio surface, lower thermal conductivity, adjustable contact angle and stable chemical nature etc., derived heat insulation, sound insulation, shockproof, close/hydrophobic, conduction, elastic and fire line etc. by these fundamental characteristics.
(2) graphene oxide provided by the present invention and graphene aerogel preparation method system, technique simply and are easily enlarged.The preparation of aeroge is with graphite oxide as presoma, by controlling character (functional group's kind and quantity, dispersibility and concentration, size, structural intergrity etc.), hydrothermal/solvent thermal process (type of solvent, reaction condition), drying process and the subsequent treatment (reduction) of graphite oxide, it is possible to obtain have graphene oxide and the graphene aerogel of specific morphology, size and excellent properties.
(3) present invention provides graphene oxide and graphene aerogel are the three-dimensional carbon materials with big pore volume and specific surface, therefore this two aerogel-like can be applied in the depollution of environment as excellent adsorbing material, repeatable utilization and regenerability are high, economic and environment-friendly.Graphene aerogel causes it huge at the application potential of electronic applications owing to having superior electric conductivity, it addition, possess excellent specific property and the graphene oxide of performance and the graphene aerogel application prospect in fields such as material, chemistry, the energy is the most boundless.
Accompanying drawing explanation
Fig. 1 is the macro morphology of graphite oxide powder.
Fig. 2 is the macro morphology of graphene oxide aeroge 1 prepared by the present invention.
Fig. 3 is the macro morphology of graphene oxide aeroge 2 prepared by the present invention.
Fig. 4 is the flexibility test experiment of graphene oxide aeroge 3 prepared by the present invention.
Fig. 5 is the water contact angle test experiments of graphene oxide aeroge 4 prepared by the present invention.
Fig. 6 is the design sketch that graphene oxide aeroge 5 prepared by the present invention adsorbs rhodamine B.
Fig. 7 is the macro morphology of graphene aerogel 1 prepared by the present invention.
Fig. 8 is the macro morphology of graphene aerogel 2 prepared by the present invention.
Fig. 9 is the fire line test experiments of graphene aerogel 3 prepared by the present invention.
Figure 10 is the water contact angle test experiments of graphene aerogel 4 prepared by the present invention.
Figure 11 is the design sketch that graphene aerogel 5 prepared by the present invention adsorbs oil refinery waste fluid.
Figure 12 is the macro morphology of graphene aerogel 6 prepared by the present invention.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1:
The synthetic method proposed according to the present invention prepares graphite oxide.
By 105 mL concentrated sulphuric acids, 1.0 g graphite and 6.5 g potassium permanganate dispersed with stirring 2.0 h under ice-water bath,；Then mixture is transferred in oil bath pan, at 36 DEG C, keeps 5 h；Reaction vessel is transferred out from oil bath pan after terminating and is rapidly added 300 mL deionized waters by process, be stirred vigorously while addition, question response system cool 98 DEG C time dropwise drip 5.0 mL hydrogen peroxide until reaction solution do not have color change and gas produce；Being 20% hydrochloric acid solution 4500 mL deionized water wash sample to after neutrality by 300 mL volume fractions successively, it is 0.3 ~ 15 that graphite oxide is configured to concentration The graphite oxide aqueous solution of mg/mL.Made graphite oxide has abundant oxygen-containing functional group, fragment, and few structure is more complete, size is fabulous at 0.5 ~ 45 μm, dispersibility.Take appropriate graphite oxide aqueous solution under the conditions of 40 DEG C, to be vacuum dried 60 h obtain graphite oxide powder as shown in Figure 1.
Embodiment 2 :
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 1.
Measure graphite oxide (a size of 0.5 ~ 3 μm) aqueous solution that 30 mL concentration are 1.0 mg/mL carry out power be 200 W, frequency be the colloid solution that ultrasonic disperse 40 min of 40 KHZ obtains graphene oxide；Transfer to graphene oxide colloid solution, in inner liner polytetrafluoroethylene reactor, at 180 DEG C, react 12 h；The graphene oxide gel that hydro-thermal reaction is obtained is washed with deionized 12 times, is-55 DEG C in cryogenic temperature, and vacuum is dry 24 h acquisition graphene oxide aeroges 1 under conditions of 1000 Pa, and its specific surface area is 299 m2/ g, macro morphology is as shown in Figure 2.
Embodiment 3 :
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 2.
Measure graphite oxide (a size of 0.5 ~ 3 μm) aqueous solution that 20 mL concentration are 1.0 mg/mL and add 10 mL ethanol preparation graphite oxide ethanol and water mixed solution carry out power be 200 W, frequency be 40 KHZ ultrasonic disperse 30 min obtains the colloid solution of graphene oxide；Transfer to graphene oxide colloid solution, in inner liner polytetrafluoroethylene reactor, at 170 DEG C, react 15 h；The graphene oxide gel that solvent thermal reaction is obtained is washed with deionized 24 times, it is-60 DEG C in cryogenic temperature, vacuum is to be dried 20 h under conditions of 1000 Pa to obtain graphene oxide aeroges 2, after measured, graphene oxide aeroge 2 density be 0.95 mg/cm3, its macro morphology is as shown in Figure 3.
Embodiment 4 :
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 3.
Measure graphite oxide (a size of 30 ~ 45 μm) aqueous solution that 10 mL concentration are 3.0 mg/mL and add 20 mL ethylene glycol preparation graphite oxide ethylene glycol and water mixed solution carry out power be 80 W, frequency be 16 KHZ ultrasonic disperse 10 min obtains the colloid solution of graphene oxide；Graphene oxide colloid solution is transferred in inner liner polytetrafluoroethylene reactor, add the PEG of 0.5% in a kettle., at 180 DEG C, react 24 h；The graphene oxide gel that solvent thermal reaction is obtained is washed with deionized 24 times, it is-65 DEG C in cryogenic temperature, vacuum is dry 48 h acquisition graphene oxide aeroges 3 under conditions of 5000 Pa, and the flexibility test of graphene oxide aeroge 3 is tested as shown in Figure 4.
Embodiment 5:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 4.
Compared with Example 2, in addition to changing the concentration (1.5 mg/mL) of graphite oxide, other are all identical with embodiment 2 for the present embodiment.The contact angle of the graphene oxide aeroge 4 obtained is 46 ° (Fig. 5).
Embodiment 6:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 5.
The present embodiment compared with Example 4, is graphite oxide aqueous solution except changing graphite oxide ethylene glycol and water mixed solution, and other are all identical with embodiment 4.It is 27 mg using prepared graphene oxide aeroge 5(mass) make filter post as filter element, prepare the rhodamine B solution of 10 mg/L, injecting 10 mL rhodamine B solution toward Filter column, solution leaches under gravity, and the rhodamine B clearance of 5 circulations is 100%(Fig. 6).
Embodiment 7:
The synthetic method proposed according to the present invention prepares graphene aerogel 1.
Measure graphite oxide (a size of 30 ~ 45 μm) aqueous solution that 2 mL concentration are 15.0 mg/mL, utilize isodensity differential centrifugation that the aqueous solvent of graphite oxide aqueous solution is carried out the displacement of ethanol, speed setting is 18000 revs/min, add ethanol after graphite oxide aqueous solution is centrifugal first to carry out high speed centrifugation and to complete ethanol, the displacement of water is prepared graphite oxide ethanol solution (constant volume to 30 mL) 20 times every time, carrying out power after graphite oxide ethanol solution dispersed with stirring 2 h to new preparation is 80 W, frequency is that 16 KHZ ultrasonic disperse 10 min obtain graphene oxide colloid ethanol solution；Graphene oxide colloid ethanol solution is transferred in inner liner polytetrafluoroethylene reactor, adds the 1H of 0.5%, 1H, 2H, 2H-the most not certain herbaceous plants with big flowers base mercaptan and the dopamine of 0.5% in a kettle., at 180 DEG C, react 12 h；Graphene (oxide) gel that solvent thermal reaction is obtained is washed with deionized 12 times repeatedly, is-60 DEG C in cryogenic temperature, and vacuum is dry 36 h acquisition Graphene (oxide) aeroges 1 under conditions of 1000 Pa；Made Graphene (oxide) aeroge is the most under an argon with the heating rate of 900 DEG C/h, and 1600 DEG C of high-temperature process 120 min i.e. can get graphene aerogel 1, and its specific surface area is 341 m2/ g, macro morphology is as shown in Figure 7.
Embodiment 8:
The synthetic method proposed according to the present invention prepares graphene aerogel 2.
Measure graphite oxide (a size of 10 ~ 20 μm) aqueous solution that 10 mL concentration are 2.7 mg/mL and add 20 mL ethanol preparation graphite oxide ethanol and water mixed solutions, to carry out power after the graphite oxide ethanol of new preparation and water mixed solution dispersed with stirring 1 h be 100 W, frequency is ethanol and the water mixed solution that 20 KHZ ultrasonic disperse 20 min obtain graphene oxide colloid；Ethanol and the water mixed solution of graphene oxide colloid are transferred in inner liner polytetrafluoroethylene reactor, adds the sucrose of 1% in a kettle., at 160 DEG C, react 24 h；Graphene (oxide) gel that solvent thermal reaction is obtained is washed with deionized 24 times repeatedly, is-58 DEG C in cryogenic temperature, and vacuum is dry 24 h acquisition Graphene (oxide) aeroges 2 under conditions of 100 Pa；Made Graphene (oxide) aeroge is vacuum dried 24 h under the conditions of 40 DEG C and i.e. can get graphene aerogel 2 after impregnating 3 h in the ammonia spirit of the 25% of 80 DEG C further, after measured, the density of graphene aerogel 2 is 0.83 mg/cm3, its macro morphology is as shown in Figure 8.
Embodiment 9:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 3.
Compared with Example 7, in addition to being vacuum dried 48 h under the conditions of 50 DEG C after changing hydroiodic acid solution impregnation 8 h of method of reduction treatment is 80 DEG C 40% of Graphene (oxide) aeroge, other are all identical with embodiment 7 for the present embodiment.The fire line test experiments of graphene aerogel 3 is as shown in Figure 9.
Embodiment 10:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 4.
Measure graphite oxide (a size of 30 ~ 45 μm) aqueous solution that 20 mL concentration are 1.75 mg/mL, utilize isodensity differential centrifugation that the aqueous solvent of graphite oxide aqueous solution is carried out the displacement of ethylene glycol, speed setting is 16000 revs/min, add ethylene glycol after graphite oxide aqueous solution is centrifugal first to carry out high speed centrifugation and to complete ethanol, the displacement of water is prepared graphite oxide ethylene glycol solution (constant volume to 35 mL) 20 times every time, carrying out power after graphite oxide ethylene glycol solution dispersed with stirring 2 h to new preparation is 80 W, frequency is that 16 KHZ ultrasonic disperse 10 min obtain graphene oxide colloid ethylene glycol solution；Graphene oxide colloid ethylene glycol solution is transferred in inner liner polytetrafluoroethylene reactor, adds the glucose of 1% in a kettle., at 190 DEG C, react 15 h；Graphene (oxide) gel that solvent thermal reaction is obtained is washed with deionized 12 times repeatedly, is-58 DEG C in cryogenic temperature, and vacuum is dry 48 h acquisition Graphene (oxide) aeroges 4 under conditions of 1500 Pa；Made Graphene (oxide) aeroge is vacuum dried 36 h after impregnating 5 h in the sodium borohydride solution of 1 g/L further under the conditions of 50 DEG C.The contact angle of the graphene aerogel 4 obtained is 122 ° (Figure 10).
Embodiment 11:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 5.
The present embodiment compared with Example 7, is that in addition to graphite oxide (a size of 30 ~ 45 μm) aqueous solution that 10 mL concentration are 2.7 mg/mL, other are all identical with embodiment 7 except changing graphite oxide aqueous solution.Adsorbing the waste oil liquid of oil plant using prepared graphene aerogel 5 as adsorbent, adsorption capacity is 106 g/g, and the adsorption capacity after 5 circulations is 103 g/g(Figure 11).
Embodiment 12:
The synthetic method proposed according to the present invention prepares graphene oxide aeroge 6.
Compared with Example 7, in addition to expanding consumption is embodiment 74 times (solvent volume of solvent thermal reaction is 120 mL) of graphite oxide aqueous solution, other are all identical with embodiment 7 for the present embodiment.The macro morphology of made graphene aerogel 6 is as shown in figure 12.

Claims (9)

1. graphene oxide (GO) and Graphene (G) aeroge and preparation method thereof and environmental applications, prepared aeroge is the carbon solid that two classes that GO with G elementary cell is constituted have a large amount of hole, similar spongiosis respectively, its preparation method includes: (1) prepares graphite oxide presoma, (2) graphite oxide character such as functional group's kind and quantity, dispersibility, concentration, dimensional structure etc. are controlled, (3) hot GO(or G of hydrothermal/solvent) solution, (4) after being dried (or being dried and reduction) process, GO(or G that i.e. availability is excellent) aeroge.
2. GO and the G aeroge described in claim 1, its preparation method is characterised by: graphite oxide solution used is the Hummer method synthesis to improve, the graphite oxide solution concentration of ultrasonic wave added preparation is 0.3 ~ 15 mg/mL, and its ultrasonic power, frequency and time are respectively 40 ~ 200 W, 8 ~ 40 KHZ and 5 ~ 120 min.
3. GO and the G aeroge described in claim 1, its preparation method is characterised by: the hot temperature and time of GO and G aeroge solvent/water is 100 ~ 200 respectively DEG C and 6 ~ 24 h, solvent/water hot afterproduct deionized water all washs 6 ~ 24 times；Lyophilization temperature, vacuum and time are-5 ~-65 DEG C, 15 ~ 60000 Pa and 1 ~ 72 h respectively.
4. the GO aeroge described in claim 1, its preparation method is characterised by: solution used is graphite oxide aqueous solution, the ethanol mixed liquor (ethanol is 0.02 ~ 2 with the volume ratio of water) with water or the mixed liquor (ethylene glycol is 0.02 ~ 2 with the volume ratio of water) of ethylene glycol and water；During GO solvent thermal, high polymer PEG, PAN and PVDF addition is 0.1 ~ 1.0 wt%.
5. the GO aeroge described in claim 4, it is characterised in that: described GO aeroge density is 0.3 ~ 2.0 mg/cm3, contact angle 30 ~ 80 °, aperture be 1 nm ~ 5 μm, porosity be 65 ~ 99%, specific surface area be 100 ~ 1700 m2/ g, GO aeroge has stronger elasticity and fire line.
6. the G aeroge described in claim 1, its preparation method is characterised by: solution used is graphite oxide ethanol solution, ethylene glycol solution, the ethanol mixed liquor (ethanol is 2 ~ 14 with the volume ratio of water) with water or the mixed liquor (ethylene glycol is 2 ~ 14 with the volume ratio of water) of ethylene glycol and water；1H in G solvent thermal process, 1H, 2H, 2H-the most not certain herbaceous plants with big flowers base mercaptan, dopamine, glucose, sucrose additive addition are 0.1 ~ 1.0 wt%；G aeroge method of reducing includes: 1) under argon shield gas 1600 ~ 2800 High-temperature process 30 ~ 240 at DEG C 300 ~ 1000 DEG C/h of min(heating rate), 2) volume ratio of 40 ~ 80 DEG C be 10 ~ 40% hydroiodic acid solution in impregnate 3 ~ 24 h, 3) volume ratio of 40 ~ 80 DEG C be 10 ~ 25% ammonia spirit in impregnate 3 ~ 24 h, or 4) sodium borohydride solution of 0.5 ~ 5 g/L impregnates under room temperature 3 ~ 24 h.
7. the G aeroge described in claim 6, it is characterised in that: described G aeroge density is 0.25 ~ 1.8 mg/cm3, contact angle 95 ~ 150 °, aperture be 1 nm ~ 3.5 μm, porosity be 80 ~ 99%, specific surface area be 300 ~ 2000 m2/ g, G aeroge has stronger elasticity and fire line.
8. the GO aeroge described in claim 1, it is characterised by environmental applications: prepared GO aeroge is used for Adsorption hydrophilic pollutant, and with prepared GO aeroge, (quality is 10 ~ 60 Mg) processing the rhodamine B solution that 5 ~ 50 mL concentration are 1 ~ 50 mg/L, rhodamine B can be by complete Adsorption；After circulating 10 times, rhodamine B clearance is still 100%.
9. the G aeroge described in claim 1, it is characterised by environmental applications: prepared G aeroge is used for Adsorption hydrophobic contaminant, and with prepared G aeroge, (quality is 10 ~ 60 Mg) adsorbing waste oil liquid in oil plant, its adsorption capacity is up to 80 g/g；After circulating 10 times, its adsorption capacity ＞ 60 g/g.
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