CN108395578A - A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane - Google Patents
A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane Download PDFInfo
- Publication number
- CN108395578A CN108395578A CN201810062657.9A CN201810062657A CN108395578A CN 108395578 A CN108395578 A CN 108395578A CN 201810062657 A CN201810062657 A CN 201810062657A CN 108395578 A CN108395578 A CN 108395578A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- fibrous
- cellulose nano
- cellulose
- composite membrane
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of cellulose nano-fibrous/graphene oxide composite membrane.Prepare cellulose nano-fibrous dispersion liquid：Hummers methods prepare graphene oxide, are then added in deionized water and are disperseed to obtain graphene oxide dispersion, i.e. GO dispersion liquids；The cellulose nano-fibrous dispersion liquid of gained is mixed with gained graphene oxide dispersion, is then stirred mixed dispersion liquid, ultrasound, cellulose nano-fibrous/graphene oxide composite membrane is made through casting film-forming and drying.The cellulose nano-fibrous graphene oxide produced with Hummers methods of TEMPO oxidative treatments is compound, OCNF is inserted into oxidized graphite flake interlayer by the effects that interlayer hydrogen bond, covalent bond, so that gained composite material with layer structure and the different quality prepared than OCNF/GO composite membranes with preferable mechanical property, and when GO contents are 10%, the tensile property of composite membrane reaches maximum value.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of cellulose nano-fibrous/graphene oxide is compound
The preparation method of film.
Background technology
Cellulose is that the maximum biomass of year output, widely distributed in nature and rich content have in the world
Also have many advantages, such as while resources advantage environmentally protective, biodegradable, nontoxic.With 2,2,6,6- tetramethyl piperidine -1- oxygen
Free radical (TEMPO) surface catalyzed oxidation can be prepared cellulose nano-fibrous (OCNF), the cellulose nanometer that this method is prepared
Fiber have good dispersibility, using its for raw material again with other substance compound tenses, by it is cellulose nano-fibrous in itself it is excellent
Mechanical property and optical property, transparent, soft and high performance thin-film material can be prepared, in recent years since it is more and more
Researcher it is of interest.
Single-layer graphene is successfully separated with the method that adhesive tape adheres to from two physicists of Univ Manchester UK, is demonstrate,proved
After graphene individualism is illustrated, scientist just pays attention in its preparation process and application again.Collect excellent electricity, optics and mechanics
The graphene of performance, rely on these advantages, can be applied to the multiple fields such as chemical industry, biology, material prepare compound,
Nanoelectronic, catalyst and its carrier etc., but graphene also has the shortcomings that poor deliquescent, so that its application is received very big
Limitation.Graphene oxide (GO) by graphene oxidation come, a large amount of oxygen-containing functional group is attached to surface after oxidation, be allowed to and
The characteristic of graphene is different.Graphene oxide has hydrophily, good can be dispersed in water, and is also dissolvable in water very much
In organic solvent, the disadvantage of graphene dissolubility difference can be made up, this is beneficial to the application of graphene oxide.However graphite oxide
Alkene film faces the defects of flexibility is poor, and mechanical property is not strong in specific application, causes its processing performance is very weak to limit
Its application range.
Invention content
Present invention aims at provide a kind of preparation side of the modified graphene oxide composite membrane of light, flexible and high mechanics
Method.
In order to achieve the above objectives, as follows using technical solution：
A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane, includes the following steps：
1) cellulose nano-fibrous dispersion liquid is prepared：
Native cellulose, TEMPO and NaBr are added in deionized water and stirred, NaClO, regulation system pH value is then added
It is 8~12, is filtered, washed after 0.5~7h of oxidation reaction at 0~40 DEG C, is dried to obtain cellulose nano-fibrous, surveyed its water and contain
Amount is 75~90wt%；It adds it to again in distilled water and is disperseed to obtain cellulose nano-fibrous dispersion liquid, i.e. OCNF points
Dispersion liquid；
2) graphene oxide dispersion is prepared：
Hummers methods prepare graphene oxide, are then added in deionized water and are disperseed to obtain graphene oxide dispersion
Liquid, i.e. GO dispersion liquids；
It is as follows that the Hummers methods prepare graphene oxide detailed process：
Reaction unit is placed in ice-water bath, wherein the concentrated sulfuric acid, potassium permanganate is added in graphite and sodium nitrate after mixing
0.5~2h is reacted, is placed it in again after reaction and stirs 3~8h in the water-bath that reaction temperature is 30~40 DEG C；Then again to body
Deionized water is added in system makes reaction temperature increase, and 0.5~2h of oxidation reaction at 85~95 DEG C；Finally restored with hydrogen peroxide
Unreacted potassium permanganate reacts 0.5~2h, the solution of glassy yellow is gradually presented；It is filtered, washed, dries after reaction
To graphene oxide；
3) cellulose nano-fibrous/graphene oxide composite membrane is prepared：
The cellulose nano-fibrous dispersion liquid of gained is mixed with gained graphene oxide dispersion, then by mixed dispersion liquid
It is stirred, ultrasound, cellulose nano-fibrous/graphene oxide composite membrane is made through casting film-forming and drying.
By said program, TEMPO, NaBr, native cellulose, NaClO are 1 in mass ratio in step 1:(1~10):(10
~100):(10~100).
By said program, the dispersing mode in step 1 includes mechanical agitation, ultrasound or one kind or more in high pressure water process
Kind.
By said program, native cellulose described in step 1 be cotton cellulose, wood pulp, flaxen fiber, bagasse, cocoanut shell,
It is one or more in shuck, wheat straw, rice bar, bacteria cellulose or ascidian cellulose.
By said program, in the cellulose nano-fibrous dispersion liquid of step 1 fibre diameter 2~20nm, length 100nm~
5μm。
By said program, graphite, sodium nitrate, the concentrated sulfuric acid and potassium permanganate are 1 in mass ratio in step 2:(1~10):(10
~100):(1~10).
By said program, the washing in step 2 is to use VH2O:VDense HCl=10:1 solution and deionized water washs three respectively
It is secondary.
The graphene oxide dispersion mass concentration is 0.1~1wt%.
By said program, graphene oxide dispersion mass concentration described in step 3 is 0.1~1wt%；The cellulose is received
A concentration of 0.1~1wt% of rice fiber dispersion；Cellulose nano-fibrous and graphene oxide is 1 in mass ratio in mixed system：
(0.1-1)。
TEMPO/NaBr/NaClO catalytic oxidation systems can carry out in aqueous solution and condition is only in normal temperature and pressure
Under, and it is environmental-friendly.Cellulose only has a small amount of energy loss, catalysis reaction to exist through TEMPO catalysis oxidation last handling processes
It is carried out in aqueous medium, at low cost and pollution is small, and TEMPO is also recyclable to be recycled, and what is obtained cellulose nano-fibrous can tie up
Hold original native cellulose shape, yield is more and size uniformity.
It is cellulose nano-fibrous that the present invention selects TEMPO methods to prepare, and method is convenient and obtains cellulose nano-fibrous straight
Diameter is small and uniform, this cellulose nano-fibrous and other polymers compound tense can play humidification.Select Hummers legal systems
The graphene oxide taken, principle are that graphite layers have introduced oxygen-containing group, and the distance between graphite flake layer and layer are because of oxygen-containing group
Group increase and can it is increasing itself can occupy certain space, the interlayer spacing of mono-layer graphite piece becomes larger, and makes interlayer Van der Waals
Power is weakened, and when to there is larger outer force effect, is detached between layers, single-layer graphene oxide is stripped out.
The beneficial effects of the present invention are：
The present invention preferably TEMPO oxidative treatments with special diameter and length it is cellulose nano-fibrous with
The graphene oxide that Hummers methods are produced is compound, and OCNF is inserted into oxidized graphite flake layer by the effects that interlayer hydrogen bond, covalent bond
Between so that gained composite material with layer structure and the different quality prepared than OCNF/GO composite membranes with preferable
Mechanical property, and when GO contents are 10%, the tensile property of composite membrane reaches maximum value.
The graphene oxide that the present invention is produced with Hummers methods because at present mainly have Staudenmaier, Brodie and
Tri- kinds of methods of Hummers prepare graphene oxide, graphene oxide made from Standenmaier and Brodie both methodss
Carbon-coating structure seriously is destroyed, and safe operation process is not high, the reaction time is longer, is unfavorable for factory's large-scale production；
And the graphene oxide reducing degree that Hummers methods are produced is minimum, operation is safer and more environmentally-friendly.
Description of the drawings
Fig. 1：The SEM of cellulose nano-fibrous/graphene oxide composite membrane (OCNF-GO10) prepared by embodiment 1 is disconnected
Face figure；
Fig. 2：The SEM cross-section diagrams of pure OCNF films prepared by comparative example 1.
Specific implementation mode
Following embodiment further illustrates technical scheme of the present invention, but not as limiting the scope of the invention.
Embodiment 1
Cellulose nano-fibrous/graphene oxide composite membrane is prepared, steps are as follows:
1) OCNF dispersion liquids are prepared:The cotton linter, 0.01g TEMPO, 0.1g NaBr for taking 2g, are added into 1000ml and go
In ionized water, 0.1g NaClO are then added into system, the NaOH solution holding system pH by the way that 0.1mol/L is added dropwise is
9, the cellulose after oxidation is filtered after reacting 5h, then is washed with deionized 3 times or more, is dried to obtain TEMPO oxidations
Cellulose；It puts it into beaker again, deionized water is added and is disperseed, then mechanical agitation 6min and supersound process 12min,
Obtain a concentration of 0.2% cellulose nano-fibrous plain dispersion liquid, i.e. 0.2%OCNF dispersion liquids.
2) GO is prepared：By 500ml three-necked flasks be placed in ice-water bath (<20 DEG C) in, 2.5g graphite, 1.875g sodium nitrate are being burnt
In bottle after mixing, 85ml concentrated sulfuric acids stirring 20min is added to be uniformly mixed, and slowly adds into mixture under agitation
Enter 12.5g potassium permanganate, reacts 0.5h；Reactant is placed in the water-bath of 35 DEG C of constant temperature later after stirring 4h into reactant
125ml deionized waters are slowly injected into, reaction temperature is risen to 90 DEG C at this time, stir 1h；It is eventually adding 30% hydrogen peroxide of 10ml,
The solution of glassy yellow is gradually presented in flask, effect is the unreacted potassium permanganate of reduction, reacts 0.5h.It is right after reaction
Product is filtered, and 10% dilute hydrochloric acid of 150ml, deionized water is used in combination to be washed respectively to it three times, and suction filtration object is then taken to be put into
In beaker, it is dispersed with stirring in 200ml deionized waters, 8000, which leave heart 30min, takes its supernatant, is installed with petri dish,
It is put into 65 DEG C of baking oven dry.
3) OCNF/GO composite membranes are prepared：By the OCNF dispersion liquids of above-mentioned preparation and GO with mass ratio 90:10 are blended,
Then mixed dispersion liquid is placed on magnetic stirrer and is stirred, duration 2h；Ultrasound 6min later centrifuges 10min bubble removings；Finally
Obtain the good OCNF/GO mixed dispersion liquids of dispersion effect.Then mixed dispersion liquid is poured into culture dish, then by culture dish 40
It is three days dry at DEG C, obtain OCNF/GO composite membranes (being denoted as OCNF-GO10).Wherein, GO accounts for the 10% of composite membrane gross mass.
Turn target X-ray diffractometer to manufactured in the present embodiment using 6700 Fourier transformation infrared spectrometers and D/MAX-RB
Functional group's type determination of OCNF-GO10 films and component, the structural information of interior atoms of substance are tested, and can be obtained compound
Film is in 3342cm-1The peaks O-H at place are to 3400cm-1It is moved at left and right (stretching vibration peak of the O-H of pure GO), and in composite membrane
OCNF is in 1608cm-1- the COO at place-1Peak is moved to high wave number, illustrates that OCNF and GO are not only that simple physics is compound, also shape
At intermolecular hydrogen bonding；The XRD spectra of composite membrane still shows the characteristic peak of OCNF, the reason is that GO contains a large amount of oxygen-containing group,
It destroys the big pi bond in graphene layer and weakens the stronger Van der Waals force of interlayer so that OCNF is easy by interlayer hydrogen bond, altogether
The effects that valence link, is inserted into oxidized graphite flake interlayer.Using RGM-4100 universal testing machines to manufactured in the present embodiment
The mechanical property of OCNF-GO10 composite membranes is tested, and the Young's modulus for measuring composite membrane is 6GPa, tensile strength 346MPa
And elongation at break is 20%, can show that OCNF-GO10 films tensile strength compared with 1 pure OCNF films of comparative example improves 48.9%
And elongation at break also improves, and illustrates that graphene oxide has humidification, the hydroxyl on the surfaces OCNF to cellulose nano-fibrous
Intermolecular hydrogen bonding is formed between the hydroxyl group of surface of graphene oxide, so that GO and OCNF is closely combined together
Layer structure is formed, good stress transfer makes composite material have higher tensile strength between GO and OCNF.
It is the SEM cross-section diagrams of OCNF-GO10 composite membranes manufactured in the present embodiment as shown in Figure 1, composite membrane as can be seen is
Toughness tension failure, rupture cross section are more coarse；And OCNF/GO laminated films have apparent layer structure, also observe that
OCNF is inserted into oxidized graphite flake interlayer.
Comparative example 1
Pure cellulose nano-cellulose film (pure OCNF films) is prepared, steps are as follows:
1) OCNF dispersion liquids are prepared:1g cotton linters, 0.01g TEMPO, 0.1g NaBr are taken, 1000ml deionized waters are added
In, then into system add 0.1g NaClO, solution system keep pH value be 9, react 5h after by the cellulose after oxidation into
Row filtering, then be washed with deionized 3 times or more, it is dried to obtain TEMPO oxycelluloses；It puts it into beaker, is added again
Deionized water is disperseed, and then mechanical agitation 6min and supersound process 12min, obtains a concentration of 0.1% cellulose nanometer
Cellulose dispersion liquid, i.e. 0.1%OCNF dispersion liquids；
2) pure OCNF films are prepared:0.1%OCNF dispersion liquids are first subjected to casting film-forming, and concentration is dried to obtain at 40 DEG C
For 0.1% pure OCNF films.
Pattern test, test knot are carried out to obtained OCNF dispersion liquids using DI Nanoscope IV atomic force microscope
Fruit shows that a diameter of 3~4nm of OCNF that this comparative example obtains, average length are 3 μm；Utilize 6700 fourier-transform infrared light
Spectrometer and D/MAX-RB turn the pure OCNF films that target X-ray diffractometer prepares this comparative example functional group's type is determining and substance
Component, the structural information of interior atoms are tested, and test result shows the infrared spectrum of pure OCNF films prepared by this comparative example
In 3342cm-1There is wide absorption peak in place, this is because the stretching vibration of O-H keys, in 1608cm-1Place is-COO-1The spy of group
Levy absorption peak ,-COO-1Group is negative electrical charge, and the mutually exclusive power between negative electrical charge and negative electrical charge makes OCNF be stably dispersed in water
In；There is an apparent diffraction maximum, (110) crystal face of corresponding cellulose I crystal, in 2 θ=24 ° in 2 θ=15 ° of XRD diagram
There is an apparent and sharp diffraction maximum, is (200) crystal face of cellulose I crystal.It is tried using RGM-4100 universal materials
The machine of testing is tested, and test result shows that the Young's modulus of pure OCNF is 5GPa, and tensile strength is 232MPa and elongation at break
It is 17%.
The SEM cross-section diagrams of the pure OCNF films of this comparative example preparation are illustrated in figure 2, pure OCNF internal structures as can be seen are in
Layer structure, and more uniformly, closely, there is only few gaps between cellulose for structure.
Embodiment 2
Cellulose nano-fibrous/graphene oxide composite membrane is prepared, steps are as follows:
1) OCNF dispersion liquids are prepared:The cotton linter, 0.01g TEMPO, 0.1g NaBr for taking 1g, are added into 1000ml and go
In ionized water, 0.1g NaClO are then added into system, it is 9 to keep system pH, by the cellulose after oxidation after reaction 5h
It is filtered, then is washed with deionized 3 times or more, be dried to obtain TEMPO oxycelluloses；It puts it into beaker, adds again
Enter deionized water to be disperseed, then mechanical agitation 6min and supersound process 12min, the cellulose for obtaining a concentration of 0.1% are received
Rice cellulose dispersion liquid, i.e. 0.1%OCNF dispersion liquids.
2) GO is prepared：By 500ml three-necked flasks be placed in ice-water bath (<20 DEG C) in, 2.5g graphite, 1.875g sodium nitrate are being burnt
In bottle after mixing, 85ml concentrated sulfuric acids stirring 20min is added to be uniformly mixed, and slowly adds into mixture under agitation
Enter 12.5g potassium permanganate, reacts 0.5h；Reactant is placed in the water-bath of 35 DEG C of constant temperature later after stirring 4h into reactant
125ml deionized waters are slowly injected into, reaction temperature is risen to 90 DEG C at this time, stir 1h；It is eventually adding 30% hydrogen peroxide of 10ml,
The solution of glassy yellow is gradually presented in flask, effect is the unreacted potassium permanganate of reduction, reacts 0.5h.It is right after reaction
Product is filtered, and 10% dilute hydrochloric acid of 150ml, deionized water is used in combination to be washed respectively to it three times, and suction filtration object is then taken to be put into
In beaker, it is dispersed with stirring in 200ml deionized waters, 8000, which leave heart 30min, takes its supernatant, is installed with petri dish,
It is put into 65 DEG C of baking oven dry.
3) OCNF/GO composite membranes are prepared：By the OCNF dispersion liquids of above-mentioned preparation and GO with mass ratio 80:20 are blended,
Then mixed dispersion liquid is placed on magnetic stirrer and is stirred, duration 2h；Ultrasound 6min later centrifuges 10min bubble removings；Finally
Obtain the good OCNF/GO mixed dispersion liquids of dispersion effect.Then mixed dispersion liquid is poured into culture dish, then culture dish is put
Enter drying three days in baking oven, obtains OCNF/GO composite membranes (being denoted as OCNF-GO20).Wherein, GO accounts for composite membrane gross mass
20%.
The mechanical property of the composite membrane prepared to this comparative example using RGM-4100 universal testing machines is tested, and is surveyed
Test result shows that the Young's modulus of OCNF-GO20 composite membranes is 6GPa, and tensile strength is 290MPa and elongation at break is
15%, it can show that composite membrane elongation at break compared with 1 pure OCNF films of comparative example is obviously reduced, illustrate that GO concentration is higher, occur
Reunite, the uniformity of composite membrane declines, and is also easy to produce stress concentration, elongation at break is caused to decline, and the brittleness of composite membrane increases.
Embodiment 3
Cellulose nano-fibrous/graphene oxide composite membrane is prepared, steps are as follows:
1) OCNF dispersion liquids are prepared:The softwood bleached pulp, 0.01g TEMPO, 0.1g NaBr for taking 3g, are added into
In 1000ml deionized waters, 0.1g NaClO are then added into system, it is 9 to keep system pH, will be after oxidation after reaction 5h
Cellulose be filtered, then be washed with deionized 3 times or more, be dried to obtain TEMPO oxycelluloses；Burning is put it into again
In cup, deionized water is added and is disperseed, then mechanical agitation 6min and supersound process 12min, obtains a concentration of 0.3% fibre
The plain nano-cellulose dispersion liquid of dimension, i.e. 0.3%OCNF dispersion liquids.
2) GO is prepared：By 500ml three-necked flasks be placed in ice-water bath (<20 DEG C) in, 5g graphite, 3.75g sodium nitrate are in flask
In after mixing, be added the 150ml concentrated sulfuric acids stirring 20min be uniformly mixed, and under agitation into mixture slowly plus
Enter 20g potassium permanganate, reacts 1h；Reactant is placed in the water-bath of 40 DEG C of constant temperature later after stirring 6h into reactant slowly
250ml deionized waters are injected, reaction temperature is risen to 90 DEG C at this time, stir 1h；It is eventually adding 30% hydrogen peroxide of 15ml, flask
In the solution of glassy yellow is gradually presented, effect is the unreacted potassium permanganate of reduction, reacts 0.5h.After reaction to product
It is filtered, 10% dilute hydrochloric acid of 180ml, deionized water is used in combination to be washed respectively to it three times, suction filtration object is then taken to be put into beaker
In, it is dispersed with stirring in 200ml deionized waters, 8000, which leave heart 30min, takes its supernatant, is installed, is put into petri dish
It is dry in 60 DEG C of baking oven.
3) OCNF/GO composite membranes are prepared：By the OCNF dispersion liquids of above-mentioned preparation and GO with mass ratio 95:5 are blended, so
Mixed dispersion liquid is placed on magnetic stirrer afterwards and is stirred, duration 2h；Ultrasound 6min later centrifuges 10min bubble removings；Final
To the good OCNF/GO mixed dispersion liquids of dispersion effect.Then mixed dispersion liquid is poured into culture dish, then culture dish is put into
In Constant Temp. Oven, drying box temperature setting is 40 DEG C, four days dry under conditions of temperature is constant, obtains OCNF/GO
Composite membrane (is denoted as OCNF-GO5).Wherein, GO accounts for the 5% of composite membrane gross mass.
Mechanics Performance Testing is carried out to composite membrane manufactured in the present embodiment using method same as Example 1, is measured multiple
The Young's modulus for closing film is 5GPa, and tensile strength is 279MPa and elongation at break is 18%, compared with 1 pure OCNF films of comparative example
Young's modulus and elongation at break are all improved, and wherein tensile strength improves 20%.
Embodiment 4
Cellulose nano-fibrous/graphene oxide composite membrane is prepared, steps are as follows:
1) OCNF dispersion liquids are prepared:0.01g TEMPO, 0.1gNaBr are taken, it is added in 1000ml deionized waters jointly,
The bacteria cellulose of 1g is added into above-mentioned system again, 0.1g NaClO are then added into system, by the way that 0.1mol/L is added dropwise
NaOH solution to keep system pH be 9, the cellulose after oxidation is filtered after reacting 5h, then is washed with deionized 3
More than secondary, it is dried to obtain TEMPO oxycelluloses；It puts it into beaker again, deionized water is added and is disperseed, it is then mechanical
It stirs 6min and is ultrasonically treated 12min, obtain a concentration of 0.1% cellulose nano-fibrous plain dispersion liquid, is i.e. 0.1%OCNF divides
Dispersion liquid.
2) GO is prepared：By 500ml three-necked flasks be placed in ice-water bath (<20 DEG C) in, 7.5g graphite, 5.625g sodium nitrate are being burnt
In bottle after mixing, 250ml concentrated sulfuric acids stirring 20min is added to be uniformly mixed, and slow into mixture under agitation
25g potassium permanganate is added, reacts 1.5h；Reactant is placed in the water-bath of 40 DEG C of constant temperature later after stirring 8h into reactant
250ml deionized waters are slowly injected into, reaction temperature is risen to 90 DEG C at this time, stir 1h；It is eventually adding 30% hydrogen peroxide of 15ml,
The solution of glassy yellow is gradually presented in flask, effect is the unreacted potassium permanganate of reduction, reacts 1h.After reaction to production
Object is filtered, and 10% dilute hydrochloric acid of 200ml, deionized water is used in combination to be washed respectively to it three times, and suction filtration object is then taken to be put into burning
In cup, it is dispersed with stirring in 200ml deionized waters, 8000, which leave heart 30min, takes its supernatant, is installed, is put with petri dish
Enter dry in 60 DEG C of baking oven.
3) OCNF/GO composite membranes are prepared：By the OCNF dispersion liquids of above-mentioned preparation and GO with mass ratio 99:1 is blended, so
Mixed dispersion liquid is placed on magnetic stirrer afterwards and is stirred, duration 2h；Ultrasound 6min later centrifuges 10min bubble removings；Final
To the good OCNF/GO mixed dispersion liquids of dispersion effect.Then mixed dispersion liquid is poured into culture dish, then culture dish is put into
In Constant Temp. Oven, drying box temperature setting is 40 DEG C, four days dry under conditions of temperature is constant, obtains OCNF/GO
Composite membrane (is denoted as OCNF-GO1).Wherein, GO accounts for the 1% of composite membrane gross mass.
Mechanics Performance Testing is carried out to composite membrane manufactured in the present embodiment using method same as Example 1, is measured multiple
The Young's modulus for closing film is 5.3GPa, and tensile strength is 275MPa and elongation at break is 17%, can obtain composite membrane and comparison
1 pure OCNF films of example increase compared to mechanical property.
Claims (8)
1. a kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane, it is characterised in that include the following steps：
1) cellulose nano-fibrous dispersion liquid is prepared：
Native cellulose, TEMPO and NaBr are added in deionized water and stirred, NaClO is then added, regulation system pH value is 8
~12, it is filtered, washed after 0.5~7h of oxidation reaction at 0~40 DEG C, is dried to obtain cellulose nano-fibrous, survey its water content
It is 75~90%；It adds it to again in distilled water and is disperseed to obtain cellulose nano-fibrous dispersion liquid；
2) graphene oxide dispersion is prepared：
Hummers methods prepare graphene oxide, are then added in deionized water and are disperseed to obtain graphene oxide dispersion；
It is as follows that the Hummers methods prepare graphene oxide detailed process：
Reaction unit is placed in ice-water bath, wherein the concentrated sulfuric acid, potassium permanganate reaction is added in graphite and sodium nitrate after mixing
0.5~2h is placed it in after reaction and is stirred 3~8h in the water-bath that reaction temperature is 30~40 DEG C again；Then again into system
Deionized water, which is added, makes reaction temperature increase, and 0.5~2h of oxidation reaction at 85~95 DEG C；It is finally restored with hydrogen peroxide not anti-
The potassium permanganate answered reacts 0.5~2h, the solution of glassy yellow is gradually presented；It is filtered, washed after reaction, is dried to obtain oxygen
Graphite alkene；
3) cellulose nano-fibrous/graphene oxide composite membrane is prepared：
The cellulose nano-fibrous dispersion liquid of gained is mixed with gained graphene oxide dispersion, then carries out mixed dispersion liquid
Cellulose nano-fibrous/graphene oxide composite membrane is made through casting film-forming and drying in stirring, ultrasound.
2. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
TEMPO, NaBr, native cellulose, NaClO are 1 in mass ratio in 1:(1~10):(10~100):(10~100).
3. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
Dispersing mode in 1 includes one or more in mechanical agitation, ultrasound or high pressure water process.
4. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
1 native cellulose is cotton cellulose, wood pulp, flaxen fiber, bagasse, cocoanut shell, shuck, wheat straw, rice bar, bacterium
It is one or more in cellulose or ascidian cellulose.
5. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
In 1 cellulose nano-fibrous dispersion liquid fibre diameter in 2~20nm, length in 100nm~5 μm.
6. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
Graphite, sodium nitrate, the concentrated sulfuric acid and potassium permanganate are 1 in mass ratio in 2:(1~10):(10~100):(1~10).
7. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
Washing in 2 is to useSolution and deionized water wash respectively three times.
8. the preparation method of cellulose nano-fibrous/graphene oxide composite membrane as described in claim 1, it is characterised in that step
The 3 graphene oxide dispersion mass concentrations are 0.1~1wt%；The cellulose nano-fibrous dispersion liquid concentration is 0.1
~1wt%；Cellulose nano-fibrous and graphene oxide is 1 in mass ratio in mixed system：(0.1-1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810062657.9A CN108395578A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810062657.9A CN108395578A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108395578A true CN108395578A (en) | 2018-08-14 |
Family
ID=63094264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810062657.9A Pending CN108395578A (en) | 2018-01-23 | 2018-01-23 | A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108395578A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369962A (en) * | 2018-10-24 | 2019-02-22 | 中国科学技术大学 | A kind of imitative clam shell feature is cellulose nano-fibrous/preparation method of black phosphorus alkene composite membrane |
| CN109880136A (en) * | 2019-02-27 | 2019-06-14 | 武汉理工大学 | A kind of preparation method of nano-cellulose/graphene nanometer sheet composite membrane |
| CN110416519A (en) * | 2019-07-31 | 2019-11-05 | 蚌埠学院 | The preparation method and application of rodlike cobalt oxide/graphene nanocomposite |
| CN110846925A (en) * | 2019-11-14 | 2020-02-28 | 华南理工大学 | Graphene-nanocellulose conductive paper and preparation method thereof |
| CN111203191A (en) * | 2020-01-16 | 2020-05-29 | 中南林业科技大学 | Preparation method of graphene oxide-doped cellulose adsorption material |
| CN111235964A (en) * | 2020-02-06 | 2020-06-05 | 中国科学院青岛生物能源与过程研究所 | Composite cellulose nano paper with single-side electric conduction, heat conduction and electromagnetic shielding function |
| CN111747724A (en) * | 2019-03-26 | 2020-10-09 | 碳星科技(天津)有限公司 | Technology for enhancing fracture strength of graphene oxide on glass microfiber membrane |
| CN111910420A (en) * | 2020-03-24 | 2020-11-10 | 贵州大学 | Method for preparing thin high-strength composite heat-conducting functional film with sandwich structure |
| CN111925542A (en) * | 2020-08-13 | 2020-11-13 | 陕西科技大学 | Anti-ultraviolet composite film and preparation method thereof |
| CN111978576A (en) * | 2020-09-07 | 2020-11-24 | 杭州肄康新材料有限公司 | Preparation method of degradable conductive composite film |
| CN112341648A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN113643906A (en) * | 2021-08-18 | 2021-11-12 | 吉林大学重庆研究院 | High-flexibility graphene-based supercapacitor based on laser processing and preparation method thereof |
| CN113652885A (en) * | 2021-07-19 | 2021-11-16 | 南京信息工程大学 | Preparation method and application of bacterial cellulose-reinforced graphene oxide paper |
| CN114149619A (en) * | 2021-12-17 | 2022-03-08 | 北京化工大学 | Preparation method of graphene/cellulose composite material |
| CN115449120A (en) * | 2022-08-22 | 2022-12-09 | 福建农林大学 | Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel |
| WO2023221279A1 (en) * | 2022-05-19 | 2023-11-23 | 浙江理工大学 | Preparation method for rgo/cnc/cnf composite thin film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101466750B1 (en) * | 2013-12-10 | 2014-11-28 | 경희대학교 산학협력단 | Graphene oxide / carboxymethylcellulose / alginate Nanocomposite |
| WO2016161491A1 (en) * | 2015-04-10 | 2016-10-13 | Universidade Estadual De Campinas-Unicamp | Method for producing transparent composite films based on graphene oxide and cellulose acetate, thus obtained transparent composite films and uses thereof |
-
2018
- 2018-01-23 CN CN201810062657.9A patent/CN108395578A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101466750B1 (en) * | 2013-12-10 | 2014-11-28 | 경희대학교 산학협력단 | Graphene oxide / carboxymethylcellulose / alginate Nanocomposite |
| WO2016161491A1 (en) * | 2015-04-10 | 2016-10-13 | Universidade Estadual De Campinas-Unicamp | Method for producing transparent composite films based on graphene oxide and cellulose acetate, thus obtained transparent composite films and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| 戴磊: "TEMPO氧化法纳米纤维素及其复合膜的制备和性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王广静等: "氧化石墨烯/纳米纤维素复合薄膜的制备及表征", 《包装工程》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369962A (en) * | 2018-10-24 | 2019-02-22 | 中国科学技术大学 | A kind of imitative clam shell feature is cellulose nano-fibrous/preparation method of black phosphorus alkene composite membrane |
| CN109369962B (en) * | 2018-10-24 | 2020-02-07 | 中国科学技术大学 | Preparation method of shell structure-imitated cellulose nanofiber/black phosphorus alkene composite membrane |
| CN109880136A (en) * | 2019-02-27 | 2019-06-14 | 武汉理工大学 | A kind of preparation method of nano-cellulose/graphene nanometer sheet composite membrane |
| CN111747724A (en) * | 2019-03-26 | 2020-10-09 | 碳星科技(天津)有限公司 | Technology for enhancing fracture strength of graphene oxide on glass microfiber membrane |
| CN110416519A (en) * | 2019-07-31 | 2019-11-05 | 蚌埠学院 | The preparation method and application of rodlike cobalt oxide/graphene nanocomposite |
| CN110846925A (en) * | 2019-11-14 | 2020-02-28 | 华南理工大学 | Graphene-nanocellulose conductive paper and preparation method thereof |
| CN111203191A (en) * | 2020-01-16 | 2020-05-29 | 中南林业科技大学 | Preparation method of graphene oxide-doped cellulose adsorption material |
| CN111235964A (en) * | 2020-02-06 | 2020-06-05 | 中国科学院青岛生物能源与过程研究所 | Composite cellulose nano paper with single-side electric conduction, heat conduction and electromagnetic shielding function |
| CN111910420A (en) * | 2020-03-24 | 2020-11-10 | 贵州大学 | Method for preparing thin high-strength composite heat-conducting functional film with sandwich structure |
| CN111925542A (en) * | 2020-08-13 | 2020-11-13 | 陕西科技大学 | Anti-ultraviolet composite film and preparation method thereof |
| CN111978576A (en) * | 2020-09-07 | 2020-11-24 | 杭州肄康新材料有限公司 | Preparation method of degradable conductive composite film |
| CN111978576B (en) * | 2020-09-07 | 2021-04-13 | 金华市星火塑料制品有限公司 | Preparation method of degradable conductive composite film |
| CN112341648A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN112341648B (en) * | 2020-10-28 | 2022-03-11 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN113652885A (en) * | 2021-07-19 | 2021-11-16 | 南京信息工程大学 | Preparation method and application of bacterial cellulose-reinforced graphene oxide paper |
| CN113643906A (en) * | 2021-08-18 | 2021-11-12 | 吉林大学重庆研究院 | High-flexibility graphene-based supercapacitor based on laser processing and preparation method thereof |
| CN114149619A (en) * | 2021-12-17 | 2022-03-08 | 北京化工大学 | Preparation method of graphene/cellulose composite material |
| WO2023221279A1 (en) * | 2022-05-19 | 2023-11-23 | 浙江理工大学 | Preparation method for rgo/cnc/cnf composite thin film |
| CN115449120A (en) * | 2022-08-22 | 2022-12-09 | 福建农林大学 | Preparation method of flame-retardant and heat-insulating sea squirt nano cellulose-based aerogel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108395578A (en) | A kind of preparation method of cellulose nano-fibrous/graphene oxide composite membrane | |
| Liu et al. | Cellulose nanopaper: fabrication, functionalization, and applications | |
| Du et al. | Sustainable valorization of paper mill sludge into cellulose nanofibrils and cellulose nanopaper | |
| Xie et al. | Preparation of thermally stable and surface-functionalized cellulose nanocrystals via mixed H2SO4/Oxalic acid hydrolysis | |
| Song et al. | Superflexible wood | |
| Qian et al. | Yarn-ball-shaped CNF/MWCNT microspheres intercalating Ti3C2Tx MXene for electromagnetic interference shielding films | |
| Spinella et al. | Concurrent cellulose hydrolysis and esterification to prepare a surface-modified cellulose nanocrystal decorated with carboxylic acid moieties | |
| Sun et al. | Comparison of highly transparent all-cellulose nanopaper prepared using sulfuric acid and TEMPO-mediated oxidation methods | |
| Juikar et al. | Extraction of nanolignin from coconut fibers by controlled microbial hydrolysis | |
| Zhou et al. | Diisocyanate modifiable commercial filter paper with tunable hydrophobicity, enhanced wet tensile strength and antibacterial activity | |
| Hossen et al. | Effect of clay content on the morphological, thermo-mechanical and chemical resistance properties of propionic anhydride treated jute fiber/polyethylene/nanoclay nanocomposites | |
| CN111154144A (en) | Preparation method of graphene oxide reinforced carbon fiber material | |
| Lu et al. | High-yield synthesis of functionalized cellulose nanocrystals for nano-biocomposites | |
| CN109880136A (en) | A kind of preparation method of nano-cellulose/graphene nanometer sheet composite membrane | |
| CN107840979A (en) | A kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| Tsou et al. | High-performance antibacterial nanocomposite films with a 3D network structure prepared from carboxylated graphene and modified polyvinyl alcohol | |
| Zhang et al. | Separation cellulose nanocrystals from microcrystalline cellulose using hydrated deep eutectic solvent and high shear force | |
| Rashid et al. | Physico-chemical characteristics of nanocellulose at the variation of catalytic hydrolysis process | |
| Rao et al. | Rapid processing of holocellulose-based nanopaper toward an electrode material | |
| Sun et al. | High-performance green electronic substrate employing flexible and transparent cellulose films | |
| Zhao et al. | Toward continuous high-performance bacterial cellulose macrofibers by implementing grading-stretching in spinning | |
| CN105884908A (en) | Preparation method of carboxylated cellulose nanoparticles | |
| Addepally et al. | Lignin-based carbon nanomaterials—the future scope | |
| Shi et al. | Scalable production of carboxylated cellulose nanofibres using a green and recyclable solvent |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180814 |