CN107265434A - A kind of bamboo nano-cellulose/redox graphene is combined the preparation method and applications of carbon aerogels - Google Patents
A kind of bamboo nano-cellulose/redox graphene is combined the preparation method and applications of carbon aerogels Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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Abstract
Prepared the invention belongs to environment functional material and pollutant process field, be related to the preparation method that a kind of bamboo nano-cellulose/redox graphene is combined carbon aerogels.Bamboo is used first for raw material, and the method peeled off by oxidation pre-treatment method and ultrasound is prepared for nano-cellulose, recycles ethylenediamine to induce bamboo nano-cellulose to be prepared for bamboo nano-cellulose/graphene oxide hydrogel with graphene oxide solution gelation；Then, the ethylenediamine for removing residual is washed, the compound carbon aerogels of low-density, hydrophobic, porous and anti-flammability bamboo nano-cellulose/redox graphene have been obtained with reference to the method for freeze-drying and high temperature pyrolysis.The material shows high adsorption capacity to oil and organic solvent pollution thing.The present invention is using inexpensively, and reproducible bamboo is as raw material, the composite carbon aerogel material excellent performance prepared, and suitable for large-scale production.
Description
Technical field
The invention belongs to the preparation of functional material and pollutant process field, it is related to a kind of bamboo nano-cellulose/reduction
Graphene oxide is combined the preparation method and applications of carbon aerogels.
Background technology
Water pollution causes serious in worldwide caused by Oil spills and the discharge of oil-containing industrial water etc.
The energy, environment and ecological problem.Adsorption technology is widely used in removing organic solvent pollution due to simple to operate and efficiency high
Thing.In recent years, performance of the porous carbon materials in terms of oil suction causes people's extensive concern.Carbon aerogels are as a kind of emerging
Porous carbon materials, with performances such as low bulk density, high voidage and surface hydrophobics, these unique physical properties can make it
Optionally adsorb oily or hydrophobic organic solvent.
Graphene is a kind of new two-dimentional carbon nanomaterial and possesses big specific surface area, high electrical conductivity and outstanding
The characteristic such as chemistry and mechanical stability, is a kind of ideal material for preparing carbon aerogels.However, scattered graphene sheet layer it
Between there is stronger active force, it is easily assembled, in addition, due to Van der Waals force between adjacent graphene sheet layer
Effect, causes that the skeleton of graphene carbon aeroge is very fragile, and mechanical performance is poor.In order to solve the above problems, at present, research
Main way be multi-component doped, can effectively be lifted graphene carbon aeroge mechanical performance and expand its application field.Receive
Rice cellulose has outstanding modulus of elasticity, it is high draw high intensity and the performance such as big specific surface area, and its surface is abundant
Surface functional group and hydrophily, make it easier to be combined with other nano materials for building new composite.
The content of the invention
The present invention is prepared for nano-cellulose, and utilize using bamboo as raw material by TEMPO oxidizing process and ultrasonic stripping method
Ethylenediamine induced oxidation graphene and nano-cellulose mixed solution formation gel, in conjunction with freeze-drying and the side of high temperature pyrolysis
Method is prepared for low-density, hydrophobic, porous and anti-flammability bamboo nanofiber/redox graphene and is combined carbon aerogels, and
For adsorbing oil and organic solvent pollution thing, high adsorption capacity is shown.Made using the nano-cellulose of biomass source
For the raw material of doping, the mechanical performance of carbon aerogels material can not only be lifted, moreover it is possible to effectively reduce graphene carbon aeroge
Prepare cost.
The present invention is achieved by the following technical solutions：
A kind of bamboo nano-cellulose/redox graphene is combined the preparation method of carbon aerogels, comprises the following steps：
Step 1, bamboo is cut into small pieces, after washing drying, recycles pulverizer grinding and sieving, bamboo powder end is made；Take
A certain amount of bamboo powder end is wrapped with filter paper, is placed in cable type extractor according, using the mixed solution of toluene and ethanol in certain temperature
Lower cyclic washing for a period of time, then dries sample；
Step 2, step 1 is obtained to sample to be added to pH is 5.0, and concentration is anti-to be carried out in 1.4% sodium chlorite solution
Should, and repeatedly, until sample becomes white；Obtained sample is added into one section of potassium hydroxide solution heating in water bath for reaction again
Time, finally reacted, and washed to neutrality, drying with 1% hydrochloric acid solution again；
Step 3, the sample dispersion for obtaining step 2 sequentially add a certain amount of sodium bromide, tetramethyl into the aqueous solution
Piperidines (TEMPO), after being mixed evenly, is added dropwise a certain amount of hypochlorite solution thereto, with sodium hydroxide or hydrochloric acid solution
PH value of solution is adjusted, and maintains pH=10.0, water-bath is carried out, reacts after terminating, then pH value of solution is adjusted to neutrality, is washed
Drying；
Step 4, the sample dispersion for obtaining step 3 stir a period of time into the aqueous solution using mixer, form uniform
Sample solution, then by solution using cell crushing instrument ultrasound a period of time, then high speed centrifugation removes unreacted solid,
Obtain the bamboo nano-cellulose solution of transparent and homogeneous；
Step 5, the bamboo nano-cellulose solution for taking step 4 to obtain add appropriate graphene oxide and second two thereto
Amine aqueous solution, mixed solution is placed in high temperature bath and reacted, and after a period of time, obtains bamboo nano-cellulose/graphene oxide
Composite aquogel, and by it under suitable bath temperature, agitator treating for a period of time, and repeatedly, to remove wherein
The ethylenediamine of residual；
After step 6, the material freeze-drying for obtaining step 5, it is placed in tube furnace, temperature programming is to heating temperature
Degree, heating carbonization a period of time, obtains nano-cellulose/redox graphene composite carbon airsetting under the conditions of high temperature nitrogen
Glue.
In step 1, sieve mesh is crossed for 40~60 mesh in bamboo powder end, the mass body of bamboo powder sample and toluene alcohol mixed solution
Product is than being 1g:The volume ratio of 20~200mL, toluene and ethanol is 2:1, wash time is 6~24h, and wash temperature is 90 DEG C.
In step 2, the mass volume ratio of sample and sodium chlorite solution are 1g:20~100mL, number of repetition is 3~8
It is secondary.
In step 2, the mass concentration of potassium hydroxide solution is 2%, and the mass volume ratio of sample and potassium hydroxide solution is
1g:20~100mL,
Add after sodium chlorite solution, 75 DEG C of reaction temperature, reaction time 1h；
Add after potassium hydroxide, water bath heating temperature is 80~95 DEG C, the heating water bath time is 2~8h；
Add after hydrochloric acid, 80 DEG C of reaction temperature, reaction time 2h.
In step 3, sample：Sodium bromide：TEMPO：The mass ratio of sodium hypochlorite is 1:0.1:0.016:0.074~0.370,
Water-bath temperature is 25 DEG C, and the water-bath time is 1~6h；Sodium hydroxide or hydrochloric acid solution used in the regulation pH value of selection
Concentration be 0.1molL-1。
In step 4, the mass concentration of sample in aqueous is 1~3%, and the speed of stirring is 8000~20000rmp,
Mixing time is 10~30min；The power of cell crushing instrument is 300~650W, and ultrasonic time is 3~10min.
In step 5, the mass concentration of bamboo nano-cellulose is 0.1%~1%, and the concentration of graphene oxide is 2g L-1,
Bamboo nano-cellulose：Graphene oxide：The mass ratio of ethylenediamine is 5:1~5：5~50, water-bath heating-up temperature be 90~
95 DEG C, the water-bath heat time is 4~10h.
In step 5, bath temperature is 20~60 DEG C during washing, and agitating mode is magnetic agitation, the speed of stirring for 100~
1000rmp, mixing time is 4~12h, and is repeated 3~9 times.
In step 6, nitrogen flow rate is 50mL min in tube furnace-1, the speed of described temperature programming is 5 DEG C of min-1, institute
The heating-up temperature stated is 800~1000 DEG C, and the duration of heat is 30~120min.
By it is above-mentioned to bamboo nano-cellulose/redox graphene be combined carbon aerogels and be used to adsorb oil or have
Machine solvent contamination thing, is comprised the following steps that：
Absorption quantity is tested：
Fritter composite carbon aerogel material is taken, weighs and records its quality, material is constantly added dropwise in oil or organic solvent
On material, until untill it can not be reabsorbed, its quality is re-recorded, composite carbon aeroge is obtained to oily or organic by calculating
The adsorption capacity of solvent.
Organic solvent pollution thing of the present invention is not only only included：Carbon tetrachloride, acetone, octane, chloroform or second
Benzene.
Beneficial effects of the present invention are：
(1) fiber content height, pigment are chosen few, it is cheap to prepare nano-cellulose as raw material with reproducible bamboo.
(2) doping of nano-cellulose can not only effectively lift the mechanical performance of redox graphene carbon aerogels,
It can also be reduced and prepare cost.
(3) ethylenediamine can effectively connect nano-cellulose and graphene oxide, be cross-linked to form plural gel.
(4) the compound carbon aerogels have the characteristics such as low-density, hydrophobic, porous and anti-flammability, adsorb it is oily with it is organic molten
High adsorption capacity and the fast rate of adsorption are shown in terms of agent.
Brief description of the drawings
Fig. 1 is the waterborne photo in kind of the present invention；
Fig. 2 schemes for the TEM of graphene oxide；
Fig. 3 schemes for the SEM of bamboo nano-cellulose/redox graphene composite aerogel.
Fig. 4 is the hydrophobic photo of compound carbon aerogels, and a is the photograph that compound carbon aerogels immersion produces minute surface phenomenon under water
Piece；B is that water droplet is in photo that is spherical and being stabilized on compound carbon aerogels surface；C is the water contact of compound carbon aerogels
Angle is characterized.
Embodiment
With reference to Figure of description and instantiation, the present invention will be further described, but protection scope of the present invention
It is not limited to this.
Embodiment 1：
1. the preparation of nano-cellulose
(1) bamboo is cut into small pieces, after washing drying, recycles pulverizer to cross 40 eye mesh screens after crushing, bamboo powder end is made；
Take 2.0g bamboo powders end to be wrapped with filter paper, be placed in cable type extractor according, be 2 using 150mL volume ratios:1 toluene is mixed with ethanol
Liquid dries sample the toluene and ethanol for removing and wherein remaining in cyclic washing 10h at 90 DEG C.
(2) taking the sample of the above-mentioned drying of 2.0g, to be added to 100mL concentration be the sodium chlorite solution that 1.4%, pH is 5.0
In, 1h is reacted at a temperature of 75 DEG C, and be repeated 5 times, drying is washed after the completion of question response.The sample 2.0g of drying is taken to add
Into solution of the 100mL concentration for 2% potassium hydroxide, 4h is reacted at 90 DEG C, after the completion of reaction, then it is molten with 1% hydrochloric acid
Liquid reacts 2h at 80 DEG C, and sample is washed till into neutrality, drying.
(3) take 1.0g samples obtained above to be added in 100mL water, and sequentially add 0.1g sodium bromide and 0.016
G TEMPO, after being well mixed, is added dropwise the formalin solution containing 0.370g sodium hypochlorite, then utilizes 0.1mol L-1's
Sodium hydroxide and hydrochloric acid solution regulation pH value of solution, during reaction is carried out, maintain 10.0,2h are reacted at a temperature of 25 DEG C, then
Mixed solution pH value is adjusted to 7.0, washing and drying.
(4) take 1.0g sample dispersions obtained above into 100mL water, make its dispersed using agitator, rotating speed is
10000rpm, mixing time is 20min, is then peeled off obtained solution using cell crushing instrument ultrasound, ultrasonic power is
500W, ultrasonic time is 5min.Then the sample after ultrasound is centrifuged, and removes the solid of residual, obtained transparent and homogeneous
Nano-cellulose solution.
2. bamboo nano-cellulose/redox graphene is combined carbon aerogels
(1) it is 2.0g L to take nano-cellulose solution that 5mL concentration obtained above is 1% and 5mL concentration-1Oxidation stone
Black alkene solution mixing, then adds 100 μ L ethylenediamine, well mixed solution is placed in the water-bath that temperature is 95 DEG C, water
The bath reaction time is 8h, washs the composite aquogel of generation in magnetic agitation in 40 DEG C of thermostat water bath after the completion of reaction
4h, rotating speed is 200rmp, and is repeated 6 times.
(2) composite aquogel after above-mentioned completion is washed is freeze-dried, in the tube furnace for being then placed on 900 DEG C,
60min is calcined under condition of nitrogen gas, nitrogen flow rate is 50mL min-1, programming rate is 5 DEG C of min-1, it is cooled to after room temperature and obtains bamboo
Nano-cellulose/redox graphene processed is combined carbon aerogels.
3. Absorption quantity is tested
Take fritter composite carbon aerogel material to be placed in culture dish, weigh and record its quality, by carbon tetrachloride solution not
It is disconnected to be added drop-wise on material, untill it can not be reabsorbed, weigh again and record its quality, Absorption quantity result shows：Bamboo
Nano-cellulose/redox graphene processed, which is combined carbon aerogels, can adsorb the carbon tetrachloride solution of 102 times of its own quality.
Embodiment 2：
1. the preparation of nano-cellulose
(1) bamboo is cut into small pieces, after washing drying, recycles pulverizer to cross 60 eye mesh screens after crushing, bamboo powder end is made；
Take 2.0g bamboo powders end to be wrapped with filter paper, be placed in cable type extractor according, be 2 using 100mL volume ratios:1 toluene is mixed with ethanol
Liquid dries sample the toluene and ethanol for removing and wherein remaining in cyclic washing 16h at 90 DEG C.
(2) taking the sample of the above-mentioned drying of 2.0g, to be added to 200mL concentration be the sodium chlorite solution that 1.4%, pH is 5.0
In, 1h is reacted at a temperature of 75 DEG C, and be repeated 3 times, drying is washed after the completion of question response.The sample 2.0g of drying is taken to add
Into solution of the 150mL concentration for 2% potassium hydroxide, 2h is reacted at 95 DEG C, after the completion of reaction, then it is molten with 1% hydrochloric acid
Liquid reacts 2h at 80 DEG C, and sample is washed till into neutrality, drying.
(3) take 1.0g samples obtained above to be added in 100mL water, and sequentially add 0.1g sodium bromide and 0.016
G TEMPO, after being well mixed, is added dropwise the formalin solution containing 0.074g sodium hypochlorite, then utilizes 0.1mol L-1's
Sodium hydroxide and hydrochloric acid solution regulation pH value of solution, during reaction is carried out, maintain 10.0,6h are reacted at a temperature of 25 DEG C, then
Mixed solution pH value is adjusted to 7.0, washing and drying.
(4) take 1.0g sample dispersions obtained above into 50mL water, make its dispersed using agitator, rotating speed is
12000rpm, mixing time is 15min, is then peeled off obtained solution using cell crushing instrument ultrasound, ultrasonic power is
600W, ultrasonic time is 3min.Then the sample after ultrasound is centrifuged, and removes the solid of residual, obtained transparent and homogeneous
Nano-cellulose solution.
2. bamboo nano-cellulose/redox graphene is combined carbon aerogels
(1) it is 2.0g L to take nano-cellulose solution that 5mL concentration obtained above is 0.5% and 5mL concentration-1Oxidation
Graphene solution is mixed, and then adds 80 μ L ethylenediamine, well mixed solution is placed in the water-bath that temperature is 95 DEG C, water
The bath reaction time is 6h, washs the composite aquogel of generation in magnetic agitation in 30 DEG C of thermostat water bath after the completion of reaction
6h, rotating speed is 100rmp, and is repeated 5 times.
(2) composite aquogel after above-mentioned completion is washed is freeze-dried, in the tube furnace for being then placed on 800 DEG C,
90min is calcined under condition of nitrogen gas, nitrogen flow rate is 50mL min-1, programming rate is 5 DEG C of min-1, it is cooled to after room temperature and obtains bamboo
Nano-cellulose/redox graphene processed is combined carbon aerogels.
3. Absorption quantity is tested
Take fritter composite carbon aerogel material to be placed in culture dish, weigh and record its quality, toluene solution is constantly dripped
It is added on material, untill it can not be reabsorbed, weighs again and record its quality, Absorption quantity result shows：It is bamboo to receive
Rice cellulose/redox graphene, which is combined carbon aerogels, can adsorb the toluene solution of 55 times of its own quality.
Embodiment 3：
1. the preparation of nano-cellulose
(1) bamboo is cut into small pieces, after washing drying, recycles pulverizer to cross 40 eye mesh screens after crushing, bamboo powder end is made；
Take 2.0g bamboo powders end to be wrapped with filter paper, be placed in cable type extractor according, be 2 using 200mL volume ratios:1 toluene is mixed with ethanol
Liquid dries sample the toluene and ethanol for removing and wherein remaining in cyclic washing 24h at 90 DEG C.
(2) taking the sample of the above-mentioned drying of 2.0g, to be added to 150mL concentration be the sodium chlorite solution that 1.4%, pH is 5.0
In, 1h is reacted at a temperature of 75 DEG C, and be repeated 6 times, drying is washed after the completion of question response.The sample 2.0g of drying is taken to add
Into solution of the 200mL concentration for 2% potassium hydroxide, 2h is reacted at 85 DEG C, after the completion of reaction, then it is molten with 1% hydrochloric acid
Liquid reacts 2h at 80 DEG C, and sample is washed till into neutrality, drying.
(3) take 1.0g samples obtained above to be added in 100mL water, and sequentially add 0.1g sodium bromide and 0.016
G TEMPO, after being well mixed, is added dropwise the formalin solution containing 0.370g sodium hypochlorite, then utilizes 0.1mol L-1's
Sodium hydroxide and hydrochloric acid solution regulation pH value of solution, during reaction is carried out, maintain 10.0,3h are reacted at a temperature of 25 DEG C, then
Mixed solution pH value is adjusted to 7.0, washing and drying.
(4) take 1.0g sample dispersions obtained above into 80mL water, make its dispersed using agitator, rotating speed is
8000rpm, mixing time is 30min, is then peeled off obtained solution using cell crushing instrument ultrasound, ultrasonic power is
300W, ultrasonic time is 10min.Then the sample after ultrasound is centrifuged, and removes the solid of residual, obtained transparent and homogeneous
Nano-cellulose solution.
2. bamboo nano-cellulose/redox graphene is combined carbon aerogels
(1) it is 2.0g L to take nano-cellulose solution that 5mL concentration obtained above is 0.1% and 5mL concentration-1Oxidation
Graphene solution is mixed, and then adds 50 μ L ethylenediamine, well mixed solution is placed in the water-bath that temperature is 90 DEG C, water
The bath reaction time is 10h, washes the composite aquogel of generation in magnetic agitation in 30 DEG C of thermostat water bath after the completion of reaction
8h is washed, rotating speed is 200rmp, and is repeated 4 times.
(2) composite aquogel after above-mentioned completion is washed is freeze-dried, in the tube furnace for being then placed on 950 DEG C,
60min is calcined under condition of nitrogen gas, nitrogen flow rate is 50mL min-1, programming rate is 5 DEG C of min-1, it is cooled to after room temperature and obtains bamboo
Nano-cellulose/redox graphene processed is combined carbon aerogels.
3. Absorption quantity is tested
Take fritter composite carbon aerogel material to be placed in culture dish, weigh and record its quality, acetone soln is constantly dripped
It is added on material, untill it can not be reabsorbed, weighs again and record its quality, Absorption quantity result shows：It is bamboo to receive
Rice cellulose/redox graphene, which is combined carbon aerogels, can adsorb the acetone soln of 44 times of its own quality.
Embodiment 4：
1. the preparation of nano-cellulose
(1) bamboo is cut into small pieces, after washing drying, recycles pulverizer to cross 60 eye mesh screens after crushing, bamboo powder end is made；
Take 2.0g bamboo powders end to be wrapped with filter paper, be placed in cable type extractor according, be 2 using 120mL volume ratios:1 toluene is mixed with ethanol
Liquid dries sample the toluene and ethanol for removing and wherein remaining in cyclic washing 18h at 90 DEG C.
(2) taking the sample of the above-mentioned drying of 2.0g, to be added to 120mL concentration be the sodium chlorite solution that 1.4%, pH is 5.0
In, 1h is reacted at a temperature of 75 DEG C, and be repeated 6 times, drying is washed after the completion of question response.The sample 2.0g of drying is taken to add
Into solution of the 120mL concentration for 2% potassium hydroxide, 2h is reacted at 90 DEG C, after the completion of reaction, then it is molten with 1% hydrochloric acid
Liquid reacts 2h at 80 DEG C, and sample is washed till into neutrality, drying.
(3) take 1.0g samples obtained above to be added in 100mL water, and sequentially add 0.1g sodium bromide and 0.016
G TEMPO, after being well mixed, is added dropwise the formalin solution containing 0.148g sodium hypochlorite, then utilizes 0.1mol L-1's
Sodium hydroxide and hydrochloric acid solution regulation pH value of solution, during reaction is carried out, maintain 10.0,2h are reacted at a temperature of 25 DEG C, then
Mixed solution pH value is adjusted to 7.0, washing and drying.
(4) take 1.0g sample dispersions obtained above into 100mL water, make its dispersed using agitator, rotating speed is
10000rpm, mixing time is 25min, is then peeled off obtained solution using cell crushing instrument ultrasound, ultrasonic power is
500W, ultrasonic time is 8min.Then the sample after ultrasound is centrifuged, and removes the solid of residual, obtained transparent and homogeneous
Nano-cellulose solution.
2. bamboo nano-cellulose/redox graphene is combined carbon aerogels
(1) it is 2.0g L to take nano-cellulose solution that 5mL concentration obtained above is 0.3% and 5mL concentration-1Oxidation
Graphene solution is mixed, and then adds 120 μ L ethylenediamine, well mixed solution is placed in the water-bath that temperature is 95 DEG C,
The water-bath time is 6h, washes the composite aquogel of generation in magnetic agitation in 20 DEG C of thermostat water bath after the completion of reaction
12h is washed, rotating speed is 400rmp, and is repeated 4 times.
(2) composite aquogel after above-mentioned completion is washed is freeze-dried, in the tube furnace for being then placed on 900 DEG C,
120min is calcined under condition of nitrogen gas, nitrogen flow rate is 50mL min-1, programming rate is 5 DEG C of min-1, it is cooled to after room temperature and obtains
Bamboo nano-cellulose/redox graphene is combined carbon aerogels.
3. Absorption quantity is tested
Take fritter composite carbon aerogel material to be placed in culture dish, weigh and record its quality, chloroformic solution is constantly dripped
It is added on material, untill it can not be reabsorbed, weighs again and record its quality, Absorption quantity result shows：It is bamboo to receive
Rice cellulose/redox graphene, which is combined carbon aerogels, can adsorb the chloroformic solution of 90 times of its own quality.
From figure 1 it appears that compound carbon aerogels can stablize bubble through the water column on, illustrate that the material has density
The stable property of small and hydrophobicity.
As can be seen from Figure 2 graphene oxide has relatively thin laminated structure, and size is about 1 microns.
As can be seen from Figure 3 it is combined in carbon aerogels and there is hole not of uniform size and uneven shape, illustrates the material
With abundant gap structure.
It can be seen that there is minute surface phenomenon on the compound carbon aerogels surface of underwater from Fig. 4 a, this is due to composite carbon airsetting
Have what air was caused between glue and the water of surrounding, illustrate that the material has excellent hydrophobic performance；Globule energy is presented in Fig. 4 b
Enough the stable surface for being present in compound carbon aerogels, also indicates that the material has hydrophobicity；Fig. 4 c are compound carbon aerogels
Water contact angle is characterized, and its water contact angle is 130o。
Claims (10)
1. a kind of bamboo nano-cellulose/redox graphene is combined the preparation method of carbon aerogels, it is characterised in that including
Following steps：
Step 1, bamboo is cut into small pieces, after washing drying, recycles pulverizer grinding and sieving, bamboo powder end is made；Take certain
The bamboo powder end of amount is wrapped with filter paper, is placed in cable type extractor according, using the mixed solution of toluene and ethanol in anti-under certain temperature
A period of time is washed in after backwashing, then dries sample；
Step 2, step 1 is obtained to sample to be added to pH is 5.0, concentration to be reacted in 1.4% sodium chlorite solution, and
Repeatedly, until sample becomes white；Obtained sample is added into potassium hydroxide solution heating in water bath for reaction for a period of time again,
Finally reacted, and washed to neutrality, drying with 1% hydrochloric acid solution again；
Step 3, the sample dispersion for obtaining step 2 sequentially add a certain amount of sodium bromide, tetramethyl piperidine into the aqueous solution
(TEMPO) after, being mixed evenly, a certain amount of hypochlorite solution is added dropwise thereto, is adjusted with sodium hydroxide or hydrochloric acid solution
PH value of solution, and pH=10.0 is maintained, water-bath is carried out, is reacted after terminating, then pH value of solution is adjusted to neutrality, washing and drying；
Step 4, the sample dispersion for obtaining step 3 stir a period of time into the aqueous solution using mixer, form uniform sample
Product solution, then by solution using cell crushing instrument ultrasound a period of time, then high speed centrifugation, removes unreacted solid, obtains
The bamboo nano-cellulose solution of transparent and homogeneous；
Step 5, the bamboo nano-cellulose solution for taking step 4 to obtain add appropriate graphene oxide thereto and ethylenediamine is molten
Liquid, mixed solution is placed in high temperature bath and reacted, after a period of time, is obtained bamboo nano-cellulose/graphene oxide and is combined
Hydrogel, and by it under suitable bath temperature, agitator treating for a period of time, and repeatedly, is wherein remained to remove
Ethylenediamine；
After step 6, the material freeze-drying for obtaining step 5, it is placed in tube furnace, temperature programming to heating-up temperature,
Heating carbonization a period of time under the conditions of high temperature nitrogen, obtain nano-cellulose/redox graphene and be combined carbon aerogels.
2. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Sieve mesh is crossed for 40~60 mesh in method, it is characterised in that in step 1, bamboo powder end, bamboo powder sample and toluene alcohol mixed solution
Mass volume ratio be 1g:The volume ratio of 20~200mL, toluene and ethanol is 2:1, wash time is 6~24h, wash temperature
For 90 DEG C.
3. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
The mass volume ratio of method, it is characterised in that in step 2, sample and sodium chlorite solution are 1g:20~100mL, number of repetition
For 3~8 times.
4. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 2, the mass concentration of potassium hydroxide solution is 2%, the quality of sample and potassium hydroxide solution
Volume ratio is 1g:20~100mL,
Add after sodium chlorite solution, 75 DEG C of reaction temperature, reaction time 1h；
Add after potassium hydroxide, water bath heating temperature is 80~95 DEG C, the heating water bath time is 2~8h；
Add after hydrochloric acid, 80 DEG C of reaction temperature, reaction time 2h.
5. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 3, sample：Sodium bromide：TEMPO：The mass ratio of sodium hypochlorite is 1:0.1:0.016:0.074
~0.370, water-bath temperature is 25 DEG C, and the water-bath time is 1~6h；Sodium hydroxide used in the regulation pH value of selection or
The concentration of hydrochloric acid solution is 0.1molL-1。
6. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 4, the mass concentration of sample in aqueous is 1~3%, the speed of stirring for 8000~
20000rmp, mixing time is 10~30min；The power of cell crushing instrument is 300~650W, and ultrasonic time is 3~10min.
7. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 5, the mass concentration of bamboo nano-cellulose is 0.1%~1%, the concentration of graphene oxide
For 2g L-1, bamboo nano-cellulose：Graphene oxide：The mass ratio of ethylenediamine is 5:1~5：5~50, water-bath heating temperature
Spend for 90~95 DEG C, the water-bath heat time is 4~10h.
8. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 5, bath temperature is 20~60 DEG C during washing, and agitating mode is magnetic agitation, the speed of stirring
Spend for 100~1000rmp, mixing time is 4~12h, and is repeated 3~9 times.
9. a kind of bamboo nano-cellulose/redox graphene according to claim 1 is combined the preparation of carbon aerogels
Method, it is characterised in that in step 6, nitrogen flow rate is 50mL min in tube furnace-1, the speed of described temperature programming is 5 DEG C
min-1, described heating-up temperature is 800~1000 DEG C, and the duration of heat is 30~120min.
10. a kind of bamboo nano-cellulose/redox graphene made from preparation method described in claim 1~10 is combined
Carbon aerogels are used for the purposes for adsorbing oil or organic solvent pollution thing.
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