CN109809396A - A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method - Google Patents

A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method Download PDF

Info

Publication number
CN109809396A
CN109809396A CN201910230548.8A CN201910230548A CN109809396A CN 109809396 A CN109809396 A CN 109809396A CN 201910230548 A CN201910230548 A CN 201910230548A CN 109809396 A CN109809396 A CN 109809396A
Authority
CN
China
Prior art keywords
aeroge
redox graphene
prepared
vapor
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910230548.8A
Other languages
Chinese (zh)
Inventor
孙航
商殷兴
秦蓁
李致远
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201910230548.8A priority Critical patent/CN109809396A/en
Publication of CN109809396A publication Critical patent/CN109809396A/en
Pending legal-status Critical Current

Links

Abstract

A kind of method that vapor hydrothermal reduction prepares redox graphene aeroge, belongs to aeroge preparation technical field.The present invention is from preparing graphene oxide aqueous dispersions, graphite oxide aerogel is prepared first with freeze-drying method, then it restores to obtain redox graphene aeroge by vapor hydro-thermal method, convenient and efficient low energy consumption is prepared for redox graphene aeroge.Redox graphene aeroge prepared by the present invention combines the excellent electric conductivity of graphene, the low energy consumption of the light porous feature of aeroge and vapor hydrothermal reduction technology, the multiple advantage such as pollution-free.The method of vacuum freeze drying used in the present invention has the advantages that easy to operate, mild condition, low in cost and technique are easy to amplify.The redox graphene aeroge of preparation can be widely applied to the fields such as water-oil separating, Adsorption of Organic, super capacitor, battery, sensing.

Description

A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method
Technical field
The invention belongs to aeroge preparation technical fields, and in particular to one kind passes through freezing using graphene oxide as raw material The redox graphene aeroge and preparation method thereof of dry and vapor hydrothermal reduction preparation.The reduction-oxidation graphite of preparation Alkene aeroge can be widely applied to the fields such as water-oil separating, Adsorption of Organic, super capacitor, battery, sensing.
Background technique
Aeroge is a kind of the light porous of the structure-controllable for mutually being coalesced by colloidal particle or the high-polymer molecule and being constituted Property solid-state material.Microcosmos network structure has hole abundant, provides big specific surface area, before it has wide application Scape has been used for acoustic impedance coupling material, catalyst or catalyst carrier, adsorbent, filtering material, high temperature insulating material and height Performance cell material, has attracted the research interest of more and more scholars in the recent period.
Graphene is a kind of new carbon, it is the single layer of carbon atom by plane with sp2Hybridized orbit forms hexangle type In the planar structure of honeycomb crystal lattice, only one carbon atom thickness is most thin material currently known in the world.Graphene It is but also most hard nano material that it is most thin, which to be currently world, it is almost fully transparent, the light of absorption 2.3%;It is thermally conductive Coefficient is up to 5300W/mK, is higher than carbon nanotube and diamond, its electron mobility is more than 15000cm under room temperature2/ Vs, It is higher than carbon nanotubes or silicon crystal, and resistivity about 10-6Ω cm, it is lower than copper or silver, it is the smallest material of world resistivity Material.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, therefore is expected to can be used to develop thinner, conductive speed faster Electronic component or transistor of new generation.Since graphene is substantially a kind of transparent, good conductor, it is saturating to be also adapted to manufacture Bright Touch Screen, tabula rasa, even solar battery.Its excellent mechanical performance, the specific surface area of superelevation, preferable heat transfer Ability, high electronic conduction ability make it in necks such as super capacitor, sensor, organization bracket, drug conduction and solar batteries Domain has become a hot topic of research.In recent years, researcher has carried out many trials in various application fields to it, but is actually answering In, due to the strong pi-pi accumulation and van der Waals interaction on graphene film surface between graphene sheet layer, occur serious irreversible Interlayer polycondensation, effective surface area greatly reduce, and limit grapheme material in the potential of the fields such as electrochemical electrode, composite material Using.Recently, by the material of two-dimensional nanoscale (such as graphene platelet) be configured to three-dimensional macro structure (such as laminar film and Porous support) it attracts wide attention, this is to explore the advanced feature of single two-dimensional slice with important one for practical application Step.
Since the preparation of graphene at this stage mainly has micromechanics partition method, chemical vapour deposition technique, low temperature thermal reduction With four kinds of methods of oxidation-reduction method.And it is micromechanics partition method low yield, at high cost, it is unsatisfactory for industrialization and large-scale production is wanted It asks, chemical vapour deposition technique can satisfy the requirement of prepare with scale high-quality graphene, but higher cost, complex process, low Warm reduction method generally takes a long time, and reduction efficiency is lower.After oxidation-reduction method is suggested, with its simple and easy technique The simplest method of graphene is prepared as laboratory, and solves graphene and is difficult to be dispersed in the problems in solvent, is obtained To the favor of vast graphene researcher, so we carry out redox graphene airsetting on the basis of oxidation-reduction method The preparation research of glue.
Redox graphene aeroge mainly has following three kinds of preparation methods at this stage, and method is first is that by cheap graphite With Hummers method oxidation removing at graphene oxide, graphene oxide dispersion is self-assembled into three by chemistry or thermal reduction Graphene network is tieed up, then by being further dried to obtain redox graphene aeroge;Method is second is that the oxidation stone that will be obtained Black alkene dispersion liquid directly freezed is dry, then obtains redox graphene aeroge by the method for strong reductant electronation; Method is freeze-dried third is that obtained graphene oxide dispersion is mixed with crosslinking agent, then by high in protective gas The method of temperature calcining obtains redox graphene aeroge.Although these three methods can largely prepare redox graphene Aeroge, but the shape of redox graphene aeroge for preparing of method one can be because can be by when Graphene gel It is shunk according to container shapes equal proportion, seriously affects the volume and density of aeroge;The reducing agent of method two is easy to bring waste liquid dirty Dye, using reducing agents such as Dimethylhydrazine, hydroquinone, sodium borohydride and liquid hydrazines, reactant or reaction product are mostly venomous injurant Matter, effect on environment are huge;The protective gas and high-temperature calcination that method three needs to flow, the at high cost of preparation, energy consumption are high, safe Coefficient is low.
There is an urgent need to develop a kind of easy mouldings out, small, easy to operate, time-consuming short, the pollution-free, cost of density at present for this field Low redox graphene aeroge preparation method.
Summary of the invention
The purpose of the present invention is to provide a kind of vapor hydrothermal reduction preparation redox graphene aeroge and its Preparation method.Redox graphene aeroge prepared by the present invention combine the excellent electric conductivity of graphene, aeroge it is light The multiple advantage such as the low energy consumption of the porous feature of matter and vapor hydrothermal reduction technology, pollution-free.Vacuum used in the present invention is cold Dry method is lyophilized, has the advantages that easy to operate, mild condition, low in cost and technique are easy to amplify.
The method that a kind of vapor hydrothermal reduction of the present invention prepares redox graphene aeroge, step is such as Under:
1) preparation of graphene oxide aqueous dispersions:
Graphene oxide is prepared with the Hummers method (ACS NANO, 2010,4 (8): 4806-4814.) of improvement Aqueous dispersions;
2) preparation of graphene oxide aeroge:
The graphene oxide aqueous dispersions that step 1) is prepared first are concentrated into 5~20mg/mL concentration, then dilute with water It releases to 3~10mg/mL concentration, then the dilution is placed in high-low temperature resistant (- 196 DEG C~250 DEG C) vessel of certain shapes It is freezed, the sample of freezing is then subjected to vacuum freeze drying again, so that the graphene oxide gas of brown be prepared Gel;
3) preparation of redox graphene aeroge:
The graphene oxide aeroge that step 2) obtains is placed in polytetrafluoroethylene (PTFE) height together with high temperature-resistant vessel It presses in reaction kettle, and aqueous solution is added in the gap between high temperature-resistant vessel and polytetrafluoroethylene (PTFE) autoclave, is not easy to wave The salting liquid of hair, not volatile aqueous slkali or not volatile acid solution, heating reaction kettle carry out vapor hydro-thermal reaction, instead Sample should be taken out after the completion, be dried in vacuo and demoulded at room temperature, to obtain the reduction-oxidation graphite of black of the present invention Alkene aeroge.
The temperature of freezing described in step 2) is -20 DEG C~-196 DEG C, and the time of freezing is 0.5~20 hour.
The temperature of vacuum freeze drying described in step 2) is -50~-80 DEG C, and the time of vacuum freeze drying is 6~48 Hour.
The temperature of hydro-thermal reaction described in step 3) is 100~250 DEG C, and the time of hydro-thermal reaction is 3~12h.
Aqueous solution described in step 3) is deionized water, tap water, river water or sodium-chloride water solution, potassium chloride is water-soluble Liquid, manganese chloride aqueous solution, ferric chloride in aqueous solution, magnesium chloride brine, calcium chloride water, aqueous sodium persulfate solution, manganese sulfate water The not volatile salting liquid such as solution, potassium sulfate solution, potassium hydroxide aqueous solution, sodium hydrate aqueous solution etc. be not volatile Aqueous slkali, dilute sulfuric acid aqueous solution etc. are not easy one of the acid solution that volatilizees.
The volatilize volume of acid solution of aqueous solution described in step 3), salting liquid, aqueous slkali or be not easy is 0.5~10mL.
Compared with existing other technologies, the present invention has the advantage that
1. graphene oxide vapor hydrothermal reduction technology of the invention is using high-temperature vapor as reducing agent, compared to A variety of reducing agents such as hydrazine hydrate, Dimethylhydrazine, hydroquinone, sodium borohydride, liquid hydrazine, hydrogen iodide, sodium hydrogensulfite, more inexpensively, Cleanliness without any pollution.
2. graphene oxide vapor hydrothermal reduction technology of the invention can obtain C/O than high under conditions of 150 DEG C Up to the graphene aerogel of 4.65:1, compared to the high-temperature calcination reduction method for needing crosslinking agent and protective gas, it is safer just Victory, cheap and low energy consumption.
3. redox graphene aeroge prepared by the present invention, during vapor hydrothermal reduction volume almost without It shrinks, compared to the redox graphene aeroge that common liq hydro-thermal method is prepared, finished product aeroge volume is big and shape Looks are more controllable.
Graphite oxide is prepared first with freeze-drying method from graphene oxide aqueous dispersions are prepared in the present invention Then alkene aeroge restores to obtain redox graphene aeroge, the system of convenient and efficient low energy consumption by vapor hydro-thermal method For redox graphene aeroge.
The equipment that the method for the present invention for preparing redox graphene aeroge uses is simple, mild condition, used Chemical reagent is cheap and easy to get.The density of aeroge can be easily adjusted by the density of the colloidal solution of freezing.Airsetting The shape of the volume and shape of glue high temperature-resistant vessel used when can be by the volume and freezing of the colloidal solution of freezing is convenient It is adjusted.The redox graphene aeroge of preparation presents microcosmic three-dimensional porous structure, the average pore size of hole It is 40~120 μm, the average length of hole wall skeleton structure is 25~95 μm, and average diameter is 1.4~9.6 μm.Present invention preparation Graphene aerogel will be with important application prospects in fields such as capacitor, catalysis, biosensor, lithium ion batteries.
Detailed description of the invention
Fig. 1: the digital phase of different volumes, redox graphene aeroge of different shapes that embodiment 1 is prepared Machine photo;(a) figure is the digital camera photo for the redox graphene aeroge being prepared using 5mL beaker as mold, (b) Figure is the number for the redox graphene aeroge being prepared using the cuboid quartz boat of 3.5 × 3.5 × 2.5cm as mold Camera photos, (c) figure is the digital camera photo for the redox graphene aeroge being prepared using 5mL test tube as mold.
Fig. 2: the electron scanning micrograph for the redox graphene aeroge that embodiment 1 is prepared;
Fig. 3: the Raman of graphite oxide aerogel and redox graphene aeroge that embodiment 1 is prepared Spectrogram;
Fig. 4: graphite oxide aerogel (a) that embodiment 1 is prepared and redox graphene aeroge (b) Carbon x-ray photoelectron spectroscopy figure;
Fig. 5: the redox graphene aeroge that embodiment 1 is prepared is to n-hexane, hexamethylene, dimethylbenzene and machine The adsorption efficiency statistical chart of oil;
Fig. 6: the digital camera photo (a) and scanning electron for the redox graphene aeroge that embodiment 2 is prepared Microscope photo (b).
Specific embodiment
More detailed description is done to technical solution of the present invention with specific embodiment below, but the example is not constituted to this The limitation of invention.
Wherein, the graphene oxide aqueous dispersions in embodiment 1-6 are made by the Hummers method of improvement, specific side Method is as follows:
1) 1g graphite powder and 13.5mL concentrated phosphoric acid (analyzing pure, mass fraction 85%) are added to (analysis of the 120mL concentrated sulfuric acid It is pure, mass fraction 98%) in.For the sake of security, this mixture is placed in the beaker of 1000mL and carries out in draught cupboard Experiment;
2) while keeping being vigorously stirred, 6g potassium permanganate is slowly added in above-mentioned suspension, the speed of charging is controlled It spends (8-10 per second), the duration that feeds is in 45min or so;
3) after adding potassium permanganate, two apertures is pricked by beaker ParafilmTM, and with tweezers, continue to be vigorously stirred;
4) persistently stir 10min after, by the mixture in 50 DEG C of oil baths heating stirring 12h.With the progress of reaction, mix Object gradually retrogradation is closed, and has a small amount of gas to emerge;
5) it after completion of the reaction, is kept stirring, is down to room temperature to temperature of reaction system, 500mL ice cube is slowly added into It states in mixture.After ice melting, suspension is in blackish green, lasting stirring;
6) remaining potassium permanganate and manganese dioxide reduction are become manganese sulfate by the hydrogen peroxide for being slowly added to 30wt.%, Until being generated without bubble.After the processing of hydrogen peroxide, suspension becomes glassy yellow, pours out supernatant after standing sedimentation;
7) hydrochloric acid of 10vol.% is added into mixture, supernatant is poured out after standing sedimentation, is repeated 3 times;Add 1 Supernatant is poured out after standing sedimentation, after being repeated 3 times, obtained graphene oxide is transferred to bag filter by the deionized water of L In, it dialyses to neutrality, it is further purified;
8) graphene oxide is diluted to a certain concentration (2~10mg mL-1), ultrasonic 5h disperses to form graphene Oxide aqueous dispersions;
9) above-mentioned graphene oxide aqueous dispersions are transferred in centrifuge tube, are centrifuged 30min under 4000rpm revolving speed, Precipitating is removed, graphene oxide aqueous dispersions, 1~9mg of concentration mL are obtained-1, can be smaller than the concentration in step 8).
Embodiment 1
1) preparation of graphene oxide aqueous dispersions:
By graphene oxide aqueous dispersions made from the above method under the conditions of 60 DEG C rotary evaporation, graphene is aoxidized Object aqueous dispersions are concentrated into 11.0mg mL-1Concentration, it is stand-by after ultrasonic disperse.
2) preparation of graphene oxide aeroge:
The graphene oxide aqueous dispersions that step 1) is prepared are diluted with water to 6mg/mL concentration, take 3mL above-mentioned Dilution is added in 5mL beaker, and 3mL dilution is separately taken to be added in 5mL test tube, then take 30mL dilution be added to 3.5 × In the cuboid quartz molds of 3.5 × 2.5cm, 12h is freezed under conditions of -20 DEG C, is then put into the sample of freezing very - 50 DEG C of freeze-drying 10h in vacuum freecing-dry machine, so that the graphene oxide gas of three kinds of browns of different shapes be prepared Gel;
3) preparation of redox graphene aeroge:
The graphene oxide aeroge that step 2) obtains is placed in 500mL polytetrafluoroethylene (PTFE) high pressure together with vessel 1mL deionized water, heating are added in gap in reaction kettle, and between high temperature-resistant vessel and polytetrafluoroethylene (PTFE) autoclave To 150 DEG C of progress vapor hydro-thermal reaction 10h, sample is taken out after the reaction was completed, and room temperature in vacuo is dry and demoulds, and obtains black Redox graphene aeroge, product density 3.77mg/cm3
Attached drawing 1 is preparation-obtained different volumes, redox graphene aeroge of different shapes in the present embodiment Digital camera photo.As shown, (a) figure is volume to be prepared by mold of 5mL beaker as 3.0cm3, quality be The cylindric redox graphene aeroge of 11.3mg, (b) figure is using the cuboid quartz boat of 3.5 × 3.5 × 2.5cm as mould It is 30.6cm that volume, which is prepared, in tool3, quality be 115.5mg cuboid redox graphene aeroge, (c) figure be with 5mL test tube is that volume is prepared is 3.0cm to mold3, quality be 11.4mg strip redox graphene aeroge.
Attached drawing 2 is the cylindric redox graphene aeroge being prepared in the present embodiment by mold of 5mL beaker Electron scanning micrograph.Three-dimensional porous structure, the average pore size of hole are all presented in very big range as shown in the figure It is 65 μm, the average length of hole wall skeleton structure is 25 μm, and average diameter is 4.2 μm.
Attached drawing 3 is preparation-obtained graphite oxide aerogel and redox graphene aeroge in the present embodiment Raman spectrogram.Characteristic peak (peak D and the G of graphite oxide aerogel and redox graphene aeroge as shown in the figure Peak) it is all high-visible, and peak value ratio (ID/IG) by 0.95 1.08 are increased to, illustrate that graphite oxide aerogel has been reduced As redox graphene aeroge.
Attached drawing 4 is preparation-obtained graphite oxide aerogel (a) and redox graphene gas in the present embodiment The carbon x-ray photoelectron spectroscopy figure of gel (b).As shown, abscissa is electron binding energy (eV), ordinate is opposite Intensity, wherein the peak at 284.5eV represents C=C key, the peak at 285.6eV represents C-C key, the peak at 286.4eV represents C- The peak that peak at O key, 286.4eV represents C=O key, the peak at 287.02eV represents at C-O-C key and 288.6eV represents O= C-O key.In Fig. 4 a, there is the peak of a large area at 287.02eV in graphite oxide aerogel, 286.4eV, 286.4eV, Also there is the peak of small area at 288.6eV, illustrate to contain in graphite oxide aerogel containing a large amount of C-O-C key and a small amount of other Oxygen functional group, and in Fig. 4 b, peak all concentrates at 284.5eV, and the intensity at other peaks is greatly lowered, and illustrates by 150 DEG C In the redox graphene aeroge sample obtained after vapor hydrothermal reduction, oxygen-containing functional group is greatly lowered, oxygen reduction The reducing degree of graphite alkene aeroge is very high.The C/O ratio that the aeroge is calculated is 4.65:1.
Attached drawing 5 is preparation-obtained redox graphene aeroge in the present embodiment to n-hexane, hexamethylene, diformazan The adsorption efficiency statistical chart of benzene and machine oil.As shown, redox graphene aeroge is to n-hexane, hexamethylene, diformazan The adsorption effect of benzene and machine oil is respectively 39.46,42.99,49.29 and 54.78 times of redox graphene aeroge self weight.
Embodiment 2 (high temperature)
Such as each step operation of embodiment 1, the difference is that the temperature of vapor hydro-thermal reaction is in the step 3) of embodiment 1 150 DEG C, the time is 10h;And the temperature of vapor hydro-thermal reaction is 200 DEG C in embodiment 2, the time is 10h.Further use phase With the volume of redox graphene aeroge that is prepared using 5mL beaker as mold of method be 2.4cm3, quality is 8.2mg, density are 3.40mg/cm3, the C/O ratio of the aeroge is 3.56:1.
Attached drawing 6 be the present embodiment in preparation-obtained redox graphene aeroge digital camera photo (a) and Electron scanning micrograph (b).As shown, (a) figure is volume to be prepared by mold of 5mL beaker as 2.4cm3, matter Amount is the cylindric redox graphene aeroge of 8.2mg, and (b) figure all presents three-dimensional porous structure in very big range, The average pore size of hole is 120 μm, and the average length of hole wall skeleton structure is 95 μm, and average diameter is 9.6 μm.
Embodiment 3 (low temperature)
Such as each step operation of embodiment 1, the difference is that the temperature of vapor hydro-thermal reaction is in the step 3) of embodiment 1 150 DEG C, the time is 10h;And the temperature of vapor hydro-thermal reaction is 100 DEG C in embodiment 3, the time is 10h.Further use phase With the volume of redox graphene aeroge that is prepared using 5mL beaker as mold of method be 3.12cm3, quality is 16.5mg, density are 5.29mg/cm3, the C/O ratio of the aeroge is 1.27:1.
Embodiment 4 (time)
Such as each step operation of embodiment 1, the difference is that the temperature of vapor hydro-thermal reaction is in the step 3) of embodiment 1 150 DEG C, the time is 10h;And the temperature of vapor hydro-thermal reaction is 150 DEG C in embodiment 4, the time is 3h.Using 5mL beaker as mould The volume for having the redox graphene aeroge being prepared is 3.016cm3, quality 12.8mg, density is 4.2mg/cm3, The C/O ratio of the aeroge is 2.27:1.
Embodiment 5 (concentration)
Such as each step operation of embodiment 1, the difference is that graphene oxide aqueous dispersions are dilute in the step 2) of embodiment 1 Release 6mg/mL;And after graphene oxide aqueous dispersions are concentrated by rotary evaporation and are used further to after 15mg/mL in embodiment 5 Continuous experiment.The body for the redox graphene aeroge for further using identical method to be prepared using 5mL beaker as mold Product is 3.21cm3, quality 29.2mg, density is 9.09mg/cm3, the C/O ratio of the aeroge is 1.99:1.
Embodiment 6 (aqueous slkali)
Such as each step operation of embodiment 1, the difference is that in high temperature-resistant vessel and polytetrafluoroethyl-ne in the step 3) of embodiment 1 1mL deionized water is added in gap between alkene autoclave;And it is high in high temperature-resistant vessel and polytetrafluoroethylene (PTFE) in embodiment 6 Press the KOH aqueous solution that 1mL, 18mg/mL are added in the gap between reaction kettle.Further use identical method with 5mL beaker The volume for the redox graphene aeroge being prepared for mold is 3.05cm3, quality 11.5mg, density is 3.77mg/cm3, the C/O ratio of the aeroge is 3.92:1.

Claims (7)

1. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge, its step are as follows:
1) preparation of graphene oxide aqueous dispersions:
Graphene oxide aqueous dispersions are prepared with the Hummers method of improvement;
2) preparation of graphene oxide aeroge:
The graphene oxide aqueous dispersions that step 1) is prepared first are concentrated into 5~20mg/mL concentration, then are diluted with water to Dilution, is then placed in vessel and freezes by 3~10mg/mL concentration, and the sample of freezing is then carried out vacuum refrigeration again It is dry, so that the graphene oxide aeroge of brown be prepared;
3) preparation of redox graphene aeroge:
The graphene oxide aeroge that step 2) obtains is placed in polytetrafluoroethylene (PTFE) autoclave together with vessel, And in the gap between high temperature-resistant vessel and polytetrafluoroethylene (PTFE) autoclave be added aqueous solution, not volatile salting liquid, Not volatile aqueous slkali or not volatile acid solution, heating carry out vapor hydro-thermal reaction, take out sample after the reaction was completed, Room temperature in vacuo is dry and demoulds, and obtains the redox graphene aeroge of black.
2. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge as described in claim 1, special Sign is: the temperature of freezing described in step 2) is -20 DEG C~-196 DEG C, and the time of freezing is 0.5~20 hour.
3. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge as described in claim 1, special Sign is: the temperature of vacuum freeze drying described in step 2) is -50~-80 DEG C, and the time of vacuum freeze drying is 6~48 small When.
4. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge as described in claim 1, special Sign is: the temperature of hydro-thermal reaction described in step 3) is 100~250 DEG C, and the time of hydro-thermal reaction is 3~12h.
5. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge as described in claim 1, special Sign is: aqueous solution described in step 3) is deionized water, tap water or river water, and not volatile salting liquid is aqueous sodium chloride Liquid, potassium chloride solution, manganese chloride aqueous solution, ferric chloride in aqueous solution, magnesium chloride brine, calcium chloride water, sodium sulphate water Solution, manganese sulfate solution or potassium sulfate solution, not volatile aqueous slkali are potassium hydroxide aqueous solution or sodium hydroxide water Solution, not volatile acid solution are dilute sulfuric acid aqueous solution.
6. a kind of method that vapor hydrothermal reduction prepares redox graphene aeroge as described in claim 1, special Sign is: aqueous solution described in step 3), not volatile salting liquid, not volatile aqueous slkali or not volatile acid solution Volume be 0.5~10mL.
7. a kind of redox graphene aeroge, it is characterised in that: be the method as described in claim 1~6 any one It is prepared.
CN201910230548.8A 2019-03-26 2019-03-26 A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method Pending CN109809396A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910230548.8A CN109809396A (en) 2019-03-26 2019-03-26 A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910230548.8A CN109809396A (en) 2019-03-26 2019-03-26 A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method

Publications (1)

Publication Number Publication Date
CN109809396A true CN109809396A (en) 2019-05-28

Family

ID=66610307

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910230548.8A Pending CN109809396A (en) 2019-03-26 2019-03-26 A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method

Country Status (1)

Country Link
CN (1) CN109809396A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110571061A (en) * 2019-08-14 2019-12-13 上海应用技术大学 Preparation method of graphene @ CoAl-LDH composite electrode material
CN112354491A (en) * 2020-10-27 2021-02-12 浙江工业大学 Carbon-nitrogen double-defect optimized three-dimensional honeycomb aerogel and preparation method and application thereof
CN112430094A (en) * 2020-11-25 2021-03-02 中国科学院上海硅酸盐研究所 Macrostructure ordered graphene aerogel and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163423A (en) * 2014-08-13 2014-11-26 东华大学 Method for preparing spongy graphene by freeze drying
CN104176729A (en) * 2014-08-12 2014-12-03 四川大学 Reduction method of oxidized graphene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104176729A (en) * 2014-08-12 2014-12-03 四川大学 Reduction method of oxidized graphene
CN104163423A (en) * 2014-08-13 2014-11-26 东华大学 Method for preparing spongy graphene by freeze drying

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘玉荣: "《碳材料在超级电容器中的应用》", 31 January 2013, 国防工业出版社 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110571061A (en) * 2019-08-14 2019-12-13 上海应用技术大学 Preparation method of graphene @ CoAl-LDH composite electrode material
CN112354491A (en) * 2020-10-27 2021-02-12 浙江工业大学 Carbon-nitrogen double-defect optimized three-dimensional honeycomb aerogel and preparation method and application thereof
CN112354491B (en) * 2020-10-27 2022-04-22 浙江工业大学 Carbon-nitrogen double-defect optimized three-dimensional honeycomb aerogel and preparation method and application thereof
CN112430094A (en) * 2020-11-25 2021-03-02 中国科学院上海硅酸盐研究所 Macrostructure ordered graphene aerogel and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106882796B (en) Preparation method of three-dimensional graphene structure/high-quality graphene
CN104477887B (en) Method for preparing graphene from microcrystalline graphite
CN104269514B (en) Possesses the preparation method of the transistion metal compound-graphene composite material of three-dimensional porous structure
CN106744841B (en) Preparation method of three-dimensional porous graphene film constructed by single-layer graphene
CN111286078A (en) Flexible conductive MXene-based foam and preparation method thereof
CN102698774B (en) Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material
CN109809396A (en) A kind of redox graphene aeroge and its vapor hydrothermal reduction preparation method
CN104773720A (en) Method for preparing single-layer molybdenum disulfide flake doped graphene composite film
WO2014032399A1 (en) Method for low-temperature preparation of graphene and of graphene-based composite material
CN107301922B (en) Three-dimensional porous graphene nano material and its preparation method and application
CN104401948A (en) Preparation method for single-layer graphite-type carbon nitride nanosheet solution
CN104817075A (en) Preparation method of highly-dispersed graphene oxide nanobelt liquid
CN103951916B (en) Polyvinylidene difluoride (PVDF) composite wave-suction material that a kind of RGO/ ferric oxide is filled and preparation method thereof
CN103466604A (en) Preparation method of porous graphene
CN104386677B (en) A kind of low-level oxidation Graphene and its preparation method
CN106783230A (en) A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof
CN104528707A (en) Preparation method of high-conductivity graphene membrane
CN103613093B (en) A kind of hydrogen reducing prepares the method for Graphene
CN105217622A (en) A kind of preparation method of controlled three-dimensional grapheme microballoon
CN112435867A (en) Preparation method of flexible self-supporting MXene/CuS supercapacitor electrode material
CN106784706A (en) A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof
CN106504907A (en) A kind of molybdenum sulfide/cobaltosic oxide composite material and its preparation method and application
CN112086297B (en) Graphene nanocarbon electrode material, preparation method and lithium ion capacitor electrode
CN104347877A (en) A nanometer level graphene-based composite material and a preparing method thereof
CN108002366B (en) Graphene solar water cleaning foam and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination