CN107089657B - A kind of activation method of graphene oxide - Google Patents
A kind of activation method of graphene oxide Download PDFInfo
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- CN107089657B CN107089657B CN201710476346.2A CN201710476346A CN107089657B CN 107089657 B CN107089657 B CN 107089657B CN 201710476346 A CN201710476346 A CN 201710476346A CN 107089657 B CN107089657 B CN 107089657B
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Abstract
The present invention provides a kind of activation methods of graphene oxide, include the following steps, after first dispersing graphene oxide in polar solvent, obtain graphene oxide solution；Then after the graphene oxide solution, activator and the acid binding agent mixing that above-mentioned steps are obtained, reaction system is obtained；Finally in the absence of oxygen, after reaction system heating reaction above-mentioned steps obtained, the graphene oxide after being activated.The present invention in a mild condition activates the hydroxyl of surface of graphene oxide, easy leaving group is formed by activator and surface of graphene oxide hydroxy combining, the carbon-oxygen bond of surface of graphene oxide is activated, reduce the difficulty of subsequent oxidation graphene surface covalent modification, a kind of higher intermediate of activity is provided for the surface-functionalized modification of graphene oxide, so that subsequent surface is modified, it can be carried out without exacting terms, save energy consumption, the lamellar structure of graphene can be kept well again, to keep the characteristic of graphene.
Description
Technical field
The invention belongs to grapheme material technical fields, are related to a kind of activation method more particularly to one of graphene oxide
The activation method of kind surface of graphene oxide hydroxyl.
Background technique
Graphene (Graphene) is a kind of new material of individual layer laminated structure being made of carbon atom.It is one kind by carbon
Atom forms the flat film that hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness with sp2 hybridized orbit.
As a kind of two dimensional crystal of only one layer of atomic thickness being made of carbon atom, it is at present into most thin in application field
Material and most tough material, 200 times more taller than steel of breaking strength, there are also elasticity well, stretch range can reach certainly
The 20% of body size；Graphene has huge theoretical specific surface area simultaneously, and physicochemical properties are stablized, can be in high working voltage
With good structural stability is kept under high current fast charging and discharging, meanwhile, graphene also has excellent electric conductivity, can drop
Low internal resistance improves the cyclical stability of supercapacitor；And if graphene can manufacture ultra micro transistor npn npn, for producing
Following supercomputer.Replace silicon with graphene, the speed of service of computer processor will be hundreds times fast；In addition, graphite
Alkene is almost fully transparent, the light of absorption 2.3%.And it is very fine and close, even the smallest gas atom (helium atom)
Also it can not penetrate.These features make it be highly suitable as the raw material of transparent electron product, such as transparent touch display screen, hair
Tabula rasa and solar panel.There is above-mentioned many excellent physical chemical property just because of graphene, in energy storage material,
Environmental project is widely used in terms of sensing sensitive, referred to as " dark fund " or " king of new material ", and before potentially applying
Scape is vast, has become global focus and research hotspot at present.
However in practical applications, there is also many problems and restraining factors, graphene easily to reunite just for graphene
It is a major obstacle for restricting graphene research and application, that there are chemical activities is weaker for the graphene of one-component, is easy hair
It is raw to reunite and the limitations such as molding not easy to be processed, so the functional modification of graphene is just particularly important in its application.
Graphene oxide is the intermediate product that oxidation-reduction method prepares graphene, has planar structure similar with graphene, but table
A large amount of oxygen-containing functional group is contained in face, such as hydroxyl, carboxyl and epoxy group, so graphene oxide has work more higher than graphene
Property, often as the modified starting material of graphene.
The functional modification of surface of graphene oxide is divided into covalent modification and the modified two large divisions of non-covalent bond, non-covalent
Key modification can keep the structure of graphene oxide well, but active force is weak, unstable, thus limit more；Covalent bond
Modified then opposing force is strong, stablizes, and is the usual approach of existing modification, can be divided into nucleophilic displacement of fluorine, parental materials, condensation instead
Should and addition reaction.But since the steric hindrance of graphene oxide is larger, so directly to the modified item of surface of graphene oxide
Part is harsh, and the reaction time is long, however curling easily occurs under severe conditions, reunites for graphene oxide, destroys its lamella knot
Structure causes its original characteristic to be destroyed.
Therefore, how a kind of method is provided, can not destroy its lamella to surface of graphene oxide stable modification
Structure, it has also become one of many forward position scientific research personnel urgent problems to be solved in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of activation method of graphene oxide, especially
A kind of activation method of surface of graphene oxide hydroxyl, the present invention in a mild condition to the hydroxyl of surface of graphene oxide into
Row activation, forms easy leaving group, obtains the carbon-oxygen bond compared with easy fracture, so that the subsequent surface carried out to graphene is modified, nothing
It needs exacting terms that can carry out, i.e. saving energy consumption, and the lamellar structure of graphene can be kept well, to keep graphene
Characteristic.
The present invention provides a kind of activation methods of graphene oxide, comprising the following steps:
A after) dispersing graphene oxide in polar solvent, graphene oxide solution is obtained；
B after the graphene oxide solution, activator and the acid binding agent mixing that) obtain above-mentioned steps, reaction system is obtained；
C) in the absence of oxygen, after reaction system heating reaction above-mentioned steps obtained, the oxidation after being activated
Graphene.
Preferably, the polar solvent includes n,N-Dimethylformamide, N-Methyl pyrrolidone, N, N- dimethylacetamide
One of amine, tetrahydrofuran, dimethyl sulfoxide and ethylene glycol are a variety of；
The acid binding agent includes one of triethylamine, pyridine and 4-dimethylaminopyridine or a variety of；
The activator includes one of paratoluensulfonyl chloride, trifluoromethanesulfanhydride anhydride, methane sulfonyl chloride and thionyl chloride
Or it is a variety of.
Preferably, the mass volume ratio of the graphene oxide and the polar solvent is (0.1~2) g:100mL；
The molar ratio of the graphene oxide and the activator is 1:(2~5)；
The molar ratio of the graphene oxide and the acid binding agent is 1:(4~10).
Preferably, the temperature of the heating reaction is 80~90 DEG C；
The time of the heating reaction is 4~10h.
Preferably, the step B) specifically:
B1) it is molten to obtain dehydration graphene oxide after dehydration for the graphene oxide solution for obtaining above-mentioned steps
Liquid；
B2) the dehydration graphene oxide solution that above-mentioned steps obtain is slowly added into the mixing of activator and polar solvent
In solution, after emptying oxygen, intermediate system is obtained；
B3) in the absence of oxygen, the mixed liquor of acid binding agent and polar solvent is slowly added into above-mentioned intermediate system,
Obtain reaction system.
Preferably, the dehydration is molecular sieve dehydration processing；
It is described to be incorporated slowly as being added dropwise；
The condition of the anaerobic includes vacuum or is passed through protective gas.
Preferably, the step A) in, the graphene oxide includes graphene oxide slurry；
The mass fraction of the graphene oxide slurry is 25%~30%；
The mass ratio of the graphene oxide slurry and the molecular sieve is 1:(10~20).
Preferably, the step C) specifically:
In the absence of oxygen, in tiny structure and in the state of be heated to reflux, reaction system that above-mentioned steps are obtained into
After row reaction, the graphene oxide after being activated is post-processed.
Preferably, the pressure of the tiny structure is 100~120mbar；
The post-processing step includes one of washing, separation and drying or a variety of；
The temperature of the drying is 50~60 DEG C；The time of the drying be 12~for 24 hours.
The present invention also provides a kind of modified graphene oxide, the activation method as described in above-mentioned technical proposal any one
Graphene oxide after obtained activation, obtains after modified.
The present invention provides a kind of activation methods of graphene oxide, include the following steps, graphene oxide exists first
After dispersing in polar solvent, graphene oxide solution is obtained；Then the graphene oxide solution that above-mentioned steps is obtained, activator
After acid binding agent mixing, reaction system is obtained；Finally in the absence of oxygen, reaction system above-mentioned steps obtained heats anti-
Ying Hou, the graphene oxide after being activated.Compared with prior art, the present invention is modified for existing surface of graphene oxide
The modified binding force of non-covalent bond is weak in method, unstable, and the technical operation of existing covalent modification surface of graphene oxide
Condition is more harsh, and temperature is high, and the reaction time is long, and energy consumption is high, cannot completely keep the lamellar structure of graphene, lead to graphene
Curling, the defect reunited.The present invention in a mild condition activates the hydroxyl of surface of graphene oxide, by activator with
Surface of graphene oxide hydroxy combining forms easy leaving group, has activated the carbon-oxygen bond of surface of graphene oxide, reduces subsequent
The difficulty of surface of graphene oxide covalent modification, the graphene oxide after being activated, the as surface of graphene oxide
Functional modification provides a kind of higher intermediate of activity.Using the graphene oxide after activation prepared by the present invention, after progress
Continuous covalent modification reaction, can carry out under the conditions of relatively mild, to keep the lamellar structure of graphene.
The present invention in a mild condition activates the hydroxyl of surface of graphene oxide, forms easy leaving group, obtains
It can carry out so that the subsequent surface carried out to graphene is modified compared with the carbon-oxygen bond of easy fracture, that is, save without exacting terms
Energy consumption, and the lamellar structure of graphene can be kept well, to keep the characteristic of graphene.
The experimental results showed that the graphene oxide after activation prepared by the present invention, surface of graphene oxide can successfully connect
Activated group is connect, and graphene sheet layer structure remains to keep well.
Detailed description of the invention
Fig. 1 is the process flow diagram of activating process shown in the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 1 prepare it is hydroxy activated after graphene oxide scanning electron microscope (SEM) photograph.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze the preparation of pure or graphene
The purity requirement of field routine.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of activation methods of graphene oxide, comprising the following steps:
A after) dispersing graphene oxide in polar solvent, graphene oxide solution is obtained；
B after the graphene oxide solution, activator and the acid binding agent mixing that) obtain above-mentioned steps, reaction system is obtained；
C) in the absence of oxygen, after reaction system heating reaction above-mentioned steps obtained, the oxidation after being activated
Graphene.
After the present invention first disperses graphene oxide in polar solvent, graphene oxide solution is obtained.
The source of the graphene oxide is not particularly limited in the present invention, with oxidation stone well known to those skilled in the art
The usual sources of black alkene, can conventionally prepare or commercially available purchase, those skilled in the art can roots
It is required according to practical condition, activation and quality control is selected and adjusted.
The form of the graphene oxide is not particularly limited in the present invention, with oxidation stone well known to those skilled in the art
The conventionally form of black alkene, can conventionally prepare or commercially available purchase, those skilled in the art can roots
It is required according to practical condition, activation and quality control is selected and adjusted, graphene oxide of the present invention preferably wraps
Graphene oxide powder or graphene oxide slurry, more preferably graphene oxide slurry are included, Shandong Ou Bo company is specifically as follows
The graphene oxide slurry (Shandong Ou Bo new material Co., Ltd patent CN106115669A) of preparation.
The concentration of the graphene oxide slurry is not particularly limited in the present invention, with oxygen well known to those skilled in the art
The concentration of graphite alkene slurry, those skilled in the art can be according to practical condition, activation requirement and quality controls
System is selected and is adjusted, and the mass fraction of graphene oxide slurry of the present invention is preferably 25%~30%, more preferably
26%~29%, more preferably 27%~28%.
The specific choice of the polar solvent is not particularly limited in the present invention, with dispersion well known to those skilled in the art
The polar solvent of graphene oxide, those skilled in the art can be according to practical condition, activation requirement and quality
Control is selected and is adjusted, and polar solvent of the present invention preferably includes n,N-Dimethylformamide (DMF), N- methylpyrrole
One of alkanone (NMP), n,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide and ethylene glycol are a variety of, more preferably
N,N-Dimethylformamide, N-Methyl pyrrolidone, tetrahydrofuran, dimethyl sulfoxide or ethylene glycol, most preferably N, N- diformazan
Base formamide.
The additional amount of the polar solvent is not particularly limited in the present invention, with oxidation stone well known to those skilled in the art
The concentration of black alkene solution, those skilled in the art can according to practical condition, activation require and quality control into
The mass volume ratio of row selection and adjustment, graphene oxide of the present invention and the polar solvent is preferably (0.1~2) g:
100mL, more preferably (0.3~1.8) g:100mL, most preferably (0.5~1.5) g:100mL.
The concrete mode of the dispersion is not particularly limited in the present invention, with dispersion well known to those skilled in the art oxidation
The mode of graphene, those skilled in the art can require according to practical condition, activation and quality control carries out
Selection and adjustment, dispersion of the present invention preferably include ultrasonic disperse.
The actual conditions of the ultrasonic disperse are not particularly limited in the present invention, with ultrasound well known to those skilled in the art
The condition of dispersion, those skilled in the art can require according to practical condition, activation and quality control is selected
It selects and adjusts, the time of dispersion of the present invention is preferably 20~60min, more preferably 25~55min, more preferably 30~
50min, most preferably 35~45min.The frequency of dispersion of the present invention is preferably 30~50KHz, more preferably 33~
48KHz, most preferably 35~45KHz.
After graphene oxide solution, activator and acid binding agent mixing that the present invention then obtains above-mentioned steps, obtain anti-
Answer system.
The specific choice of the activator is not particularly limited in the present invention, with activator well known to those skilled in the art
, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted, this
It invents the activator and preferably includes paratoluensulfonyl chloride (TosCl), trifluoromethanesulfanhydride anhydride (Tf2O), methane sulfonyl chloride (MSCl)
With one of thionyl chloride or a variety of, more preferably paratoluensulfonyl chloride, trifluoromethanesulfanhydride anhydride, methane sulfonyl chloride or dichloro are sub-
Sulfone, most preferably paratoluensulfonyl chloride.
The dosage of the activator is not particularly limited in the present invention, conventional with activator well known to those skilled in the art
Dosage, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted
Whole, the molar ratio of graphene oxide of the present invention and the activator is preferably 1:(2~5), more preferably 1:(2.5~
4.5), most preferably 1:(3~4).
The specific choice of the acid binding agent is not particularly limited in the present invention, with acid binding agent well known to those skilled in the art
, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted, this
It invents the acid binding agent and preferably includes one of triethylamine, pyridine and 4-dimethylaminopyridine or a variety of, more preferably three second
Amine or pyridine, most preferably triethylamine.
The dosage of the acid binding agent is not particularly limited in the present invention, conventional with acid binding agent well known to those skilled in the art
Dosage, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted
Whole, the molar ratio of graphene oxide of the present invention and the acid binding agent is preferably 1:(4~10), more preferably 1:(5~9),
Most preferably 1:(6~8).
The present invention is to further increase the performance of the graphene oxide after activation, complete process route, the step B) tool
Body is preferred are as follows:
B1) it is molten to obtain dehydration graphene oxide after dehydration for the graphene oxide solution for obtaining above-mentioned steps
Liquid；
B2) the dehydration graphene oxide solution that above-mentioned steps obtain is slowly added into the mixing of activator and polar solvent
In solution, after emptying oxygen, intermediate system is obtained；
B3) in the absence of oxygen, the mixed liquor of acid binding agent and polar solvent is slowly added into above-mentioned intermediate system,
Obtain reaction system.
The present invention is to avoid the influence of water in graphene raw material and polar solvent in system, preferably obtains above-mentioned steps
Graphene oxide solution obtains dehydration graphene oxide solution after dehydration.
The concrete mode of the dehydration is not particularly limited in the present invention, with dehydration well known to those skilled in the art
Processing mode, those skilled in the art can control according to practical condition, moisture content of raw material and quality and carry out
Selection and adjustment, dehydration of the present invention are preferably molecular sieve dehydration processing, i.e., are carried out dehydrating using molecular sieve, more
It is preferably carried out dehydrating using 5A molecular sieve, is specifically as follows and mistake after immersion is added in graphene oxide solution in molecular sieve
Filter processing.
The dosage of the molecular sieve is not particularly limited in the present invention, is with conventional amount used well known to those skilled in the art
Can, those skilled in the art can control according to practical condition, moisture content of raw material and quality and select and adjust,
The mass ratio of the quality of molecular sieve of the present invention and the graphene oxide slurry is preferred (10~20): 1, more preferably (12
~18): 1, more preferably (14~16): 1.
The time of the dehydration is not particularly limited in the present invention, with dewatering time well known to those skilled in the art
, those skilled in the art can according to practical condition, moisture content of raw material and quality control select and adjust
Whole, the time of dehydration of the present invention is preferably 12~48h, more preferably 18~42h, most preferably 24~36h.
The present invention is to avoid the influence of oxygen in air, unevenly, preferably will be above-mentioned also to avoid activation process unstable
The dehydration graphene oxide solution that step obtains is slowly added into the mixed solution of activator and polar solvent, empties oxygen
Afterwards, intermediate system is obtained, i.e., is preferably first mixed activator with polar solvent, obtains mixed solution, then above-mentioned steps are obtained
Dehydration graphene oxide solution be slowly added in mixed solution, empty oxygen after, obtain intermediate system.
The specific ratio of the mixed solution is not particularly limited in the present invention, with routine well known to those skilled in the art
Ratio, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted
Whole, the present invention can be fully dispersed with activator or be dissolved in polar solvent as preferred embodiment.
The mode being slowly added to is not particularly limited in the present invention, is slowly added to well known to those skilled in the art
Mode, those skilled in the art can according to practical condition, activation require and quality control select and
Adjustment, the mode of the present invention being slowly added to preferably include to be added dropwise.
The actual conditions being slowly added to are not particularly limited in the present invention, with well known to those skilled in the art slow
The condition of addition, those skilled in the art can require according to practical condition, activation and quality control is selected
It selects and adjusts, the rate of the present invention being slowly added to is preferably 1~2 drop/sec, more preferably 1 drop/sec or 2 drops/sec.
The mode of the emptying oxygen is not particularly limited in the present invention, with emptying oxygen well known to those skilled in the art
Mode, those skilled in the art can according to practical condition, activation require and quality control select and
The mode of adjustment, emptying oxygen of the present invention preferably includes vacuum and/or is passed through protective gas, is more preferably passed through protection
Property gas, is specifically as follows and is passed through nitrogen.
The present invention is to avoid the influence of oxygen in air, also to avoid activation process unstable, unevenly, preferably in anaerobic
Under conditions of, the mixed liquor of acid binding agent and polar solvent is slowly added into above-mentioned intermediate system, reaction system is obtained, i.e., it is excellent
Choosing first mixes acid binding agent with polar solvent, obtains mixed liquor, then in the absence of oxygen, be slowly added into above-mentioned steps
In obtained intermediate system, after emptying oxygen, reaction system is obtained.
The present invention has special limitation to the specific ratio of the mixed liquor, with conventional ratio well known to those skilled in the art
, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted, this
Invention can be fully dispersed with acid binding agent or be dissolved in polar solvent as preferred embodiment.
The mode being slowly added to is not particularly limited in the present invention, is slowly added to well known to those skilled in the art
Mode, those skilled in the art can according to practical condition, activation require and quality control select and
Adjustment, the mode of the present invention being slowly added to preferably include to be added dropwise.
The actual conditions being slowly added to are not particularly limited in the present invention, with well known to those skilled in the art slow
The condition of addition, those skilled in the art can require according to practical condition, activation and quality control is selected
It selects and adjusts, the rate of the present invention being slowly added to is preferably 1~2 drop/sec, more preferably 1 drop/sec or 2 drops/sec.
The producing method under conditions of the anaerobic is not particularly limited in the present invention, with well known to those skilled in the art
Empty oxygen mode, those skilled in the art can according to practical condition, activation require and quality control into
Row selection and adjustment, the condition of anaerobic of the present invention preferably include vacuum and/or are passed through protective gas, be more preferably passed through
Protective gas is more preferably passed through nitrogen or inert gas, is specifically as follows and is passed through nitrogen.
The present invention finally in the absence of oxygen, after the reaction system heating reaction that above-mentioned steps are obtained, is activated
Graphene oxide afterwards.
The producing method under conditions of the anaerobic is not particularly limited in the present invention, with well known to those skilled in the art
Empty oxygen mode, those skilled in the art can according to practical condition, activation require and quality control into
Row selection and adjustment, the condition of anaerobic of the present invention preferably include vacuum and/or are passed through protective gas, be more preferably passed through
Protective gas is specifically as follows and is passed through nitrogen.
The temperature of the heating reaction is not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, activation require and quality control is selected and adjusted, and the temperature of heating reaction of the present invention is preferably 80~90
DEG C, more preferably 82~88 DEG C, most preferably 84~86 DEG C.The time of the heating reaction is not particularly limited in the present invention,
Those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted, the present invention
The time of the heating reaction is preferably 4~10h, more preferably 5~9h, most preferably 6~8h.
The present invention is to further increase the performance of the graphene oxide after activation, complete process route, the step C) tool
Body is preferred are as follows:
In the absence of oxygen, in tiny structure and in the state of be heated to reflux, reaction system that above-mentioned steps are obtained into
After row reaction, the graphene oxide after being activated is post-processed.
The specific pressure of the tiny structure is not particularly limited in the present invention, with tiny structure well known to those skilled in the art
Pressure, those skilled in the art can according to practical condition, activation require and quality control select and
Adjustment, the pressure of tiny structure of the present invention is preferably 100~120mbar, more preferably 105~115mbar, more preferably
108~112mbar is specifically as follows 100mbar.
The specific steps of the post-processing are not particularly limited in the present invention, after routine well known to those skilled in the art
Processing step, those skilled in the art can require according to practical condition, activation and quality control selects
And adjustment, post-processing step of the present invention preferably include one of washing, separation and drying or a variety of, more preferably wash
It washs, separate and dries, be specifically as follows filtering and washing, separation and vacuum drying.
The actual conditions of the drying are not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, activation require and quality control is selected and adjusted, and the temperature of drying of the present invention is preferably 50~60 DEG C, more
Preferably 52~58 DEG C, more preferably 54~56 DEG C, are specifically as follows 55~60 DEG C.The time of drying of the present invention is preferably
12~for 24 hours, and more preferably 15~21h, more preferably 17~20h, it is specifically as follows 18~for 24 hours.
The present invention is further complete process route, refines activation process, and above-mentioned activation method is specifically as follows:
1) graphene oxide slurry is distributed in polar solvent, obtains graphene oxide solution；
2) graphene oxide solution obtained in step 1) carries out ultrasonic disperse processing；
3) 5A molecular sieve is added to filtration treatment after impregnating in graphene oxide solution obtained in step 2)；
4) a certain amount of activator is dissolved into polar solvent, obtains mixed liquor；
5) it is slowly dropped in mixed liquor obtained in step 4), obtains into graphene oxide solution obtained in step 3)
To intermediate system；
6) intermediate system will be obtained in step 5) to be added in three-necked flask, be connected on biexhaust pipe, lead to nitrogen 20min；
7) a certain amount of acid binding agent is dissolved into polar solvent, obtains mixed liquor；
8) lead in the intermediate system that the mixed liquor for obtaining step 7) under condition of nitrogen gas is slowly dropped in step 6), obtain
Reaction system；
9) reaction system is taken out into negative pressure to 100mbar using diaphragm pump；
10) reaction system is heated, guarantees solvent refluxing；
11) by after the separation of black product filtering and washing obtained in step 10), vacuum drying obtains surface hydroxyl activation
Graphene oxide afterwards.
Above-mentioned steps of the present invention provide a kind of activation method of surface of graphene oxide hydroxyl, it is intended to be graphene oxide
Surface-functionalized modification a kind of higher intermediate of activity is provided, i.e., the graphene oxide after the described activation preferably refers to modification
The presoma of graphene oxide.The present invention further passes through preferred specific activator and surface of graphene oxide hydroxy combining shape
At easy leaving group, the carbon-oxygen bond of surface of graphene oxide has been activated, has reduced the difficulty of surface of graphene oxide covalent modification
Degree.Again particularly preferably by tiny structure, so that reaction system forms slight boiling condition, promote oxidant and oxidation in a manner of reflux
Graphene surface contact, shortens the reaction time, reduces reaction temperature.It is subsequent with hydroxy activated oxidation prepared by the present invention
Graphene is the process that raw material carries out functional modification, and mild condition, graphene can keep slab organization well, thus more
The characteristic of graphene is kept well.
The present invention also provides a kind of modified graphene oxide, the activation method as described in above-mentioned technical proposal any one
Graphene oxide after obtained activation, obtains after modified.
The concrete mode of the modification is not particularly limited in the present invention, with conventional oxygen well known to those skilled in the art
Graphite alkene surface modification mode, those skilled in the art can be according to practical condition, modified requirement and quality
Control is selected and is adjusted, and modification of the present invention is preferably that surface is modified, more preferably surface covalent modification.
The present invention provides a kind of activation methods of graphene oxide, in a mild condition to the hydroxyl of surface of graphene oxide
Base is activated, and further forms easy leaving group by preferred specific activator and surface of graphene oxide hydroxy combining,
The carbon-oxygen bond for having activated surface of graphene oxide reduces the difficulty of surface of graphene oxide covalent modification.Again particularly preferably
Oxidant is promoted to connect with surface of graphene oxide in a manner of reflux so that reaction system forms slight boiling condition by tiny structure
Touching, shortens the reaction time, reduces reaction temperature, the graphene oxide after being activated, the as table of graphene oxide
Face functional modification provides a kind of higher intermediate of activity or presoma.Using the graphite oxide after activation prepared by the present invention
Alkene carries out subsequent covalent modification reaction, can carry out under the conditions of relatively mild, to keep the lamella of graphene
Structure.
The present invention in a mild condition activates the hydroxyl of surface of graphene oxide, forms easy leaving group, obtains
It can carry out so that the subsequent surface carried out to graphene is modified compared with the carbon-oxygen bond of easy fracture, that is, save without exacting terms
Energy consumption, and the lamellar structure of graphene can be kept well, to keep the characteristic of graphene.
The experimental results showed that the graphene oxide after activation prepared by the present invention, surface of graphene oxide can successfully connect
Activated group is connect, and graphene sheet layer structure remains to keep well.
In order to further illustrate the present invention, with reference to embodiments to a kind of activation of graphene oxide provided by the invention
Method is described in detail, but it is to be understood that and these embodiments are to be implemented under the premise of the technical scheme of the present invention,
The detailed implementation method and specific operation process are given, only to further illustrate the features and advantages of the present invention, without
It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
1. 0.75g graphene oxide slurry (mass fraction 28%) is added in single-necked flask, 100mL DMF is added, surpasses
Sound stirring 30min obtains graphene oxide dispersion；
2. the 5A molecular sieve after 9g activation is added in step 1. middle graphene oxide dispersion, dispersion liquid after impregnating for 24 hours
It is filled into three-necked flask；
3. weighing 1.14g paratoluensulfonyl chloride (paratoluensulfonyl chloride is 3:1 with graphene oxide molar ratio), 10mL is added
DMF dissolution；
4. under stirring condition, by step 3. obtained in solution be slowly dropped to step 2. obtained in graphene oxide point
In dispersion liquid；
5. step 4. in be transferred in oil bath pan equipped with the three-necked flask of dispersion liquid, connect condenser pipe, biexhaust pipe, lead to nitrogen
20min；
6. weighing 1.212g triethylamine (triethylamine is 6:1 with graphene oxide molar ratio), 10mLDMF dissolution is added；
7. under condition of nitrogen gas, 6. solution that step is obtained is added drop-wise in 5. dispersion liquid that step obtains, 10min is stirred；
8. after completing step 7., disconnecting biexhaust pipe, reaction system closing, condenser pipe connects diaphragm pump, takes out negative pressure
100mbar；
9. opening heating, it is heated to reflux 6h at 80 DEG C, product filters after the reaction was completed, DMF washing, 80 DEG C of vacuum drying
12h, obtain it is hydroxy activated after graphene oxide.
It is the process flow diagram of activating process shown in the embodiment of the present invention 1 referring to Fig. 1, Fig. 1.
Member is carried out using elemental analyser method to the graphene oxide after hydroxy activated prepared by the embodiment of the present invention 1
Element analysis.
Referring to table 1, table 1 is the graphene oxide elemental analysis result of the activation of the embodiment of the present invention 1~4 front and back.
Table 1
| Project | Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| C/% | 54.87 | 60.1 | 52.05 | 56.46 | 55.21 |
| H/% | 2.12 | 2.959 | 2.04 | 2.34 | 2.15 |
| O/% | 38.698 | 30.0810 | 30.1542 | 31.2526 | 31.2500 |
| N/% | 0.08 | 1.38 | 1.35 | 1.42 | 1.30 |
| S/% | 0.660 | 1.087 | 1.256 | 1.145 | 1.150 |
As can be seen from Table 1, each embodiment product sulfur content compared with raw material is significantly raised, illustrates activator
It is connected to surface of graphene oxide.
Graphene oxide after the surface hydroxyl activation prepared to the embodiment of the present invention 1 characterizes.
Referring to fig. 2, Fig. 2 be the embodiment of the present invention 1 prepare it is hydroxy activated after graphene oxide scanning electron microscope (SEM) photograph.
As seen from Figure 2, the graphene oxide after activation still exists with sheet, can be very good to keep lamella knot
Structure.
Embodiment 2
1. 0.75g graphene oxide slurry (mass fraction 28%) is added in single-necked flask, 100mL DMF is added, surpasses
Sound stirring 30min obtains graphene oxide dispersion；
2. the 5A molecular sieve after 9g activation is added in step 1. middle graphene oxide dispersion, dispersion liquid after impregnating for 24 hours
It is filled into three-necked flask；
3. weighing 1.128g trifluoromethanesulfanhydride anhydride (trifluoromethanesulfanhydride anhydride is 2:1 with graphene oxide molar ratio), it is added
10mL DMF dissolution；
4. under stirring condition, by step 3. obtained in solution be slowly dropped to step 2. obtained in graphene oxide point
In dispersion liquid；
5. step 4. in be transferred in oil bath pan equipped with the three-necked flask of dispersion liquid, connect condenser pipe, biexhaust pipe, lead to nitrogen
20min；
6. weighing 0.808g triethylamine (triethylamine is 4:1 with graphene oxide molar ratio), 10mLDMF dissolution is added；
7. under condition of nitrogen gas, 6. solution that step is obtained is added drop-wise in 5. dispersion liquid that step obtains, 10min is stirred；
8. after completing step 7., disconnecting biexhaust pipe, reaction system closing, condenser pipe connects diaphragm pump, takes out negative pressure
100mbar；
9. opening heating, it is heated to reflux 6h at 80 DEG C, product filters after the reaction was completed, DMF washing, 80 DEG C of vacuum drying
12h, obtain it is hydroxy activated after graphene oxide.
Embodiment 3
1. 0.75g graphene oxide slurry (mass fraction 28%) is added in single-necked flask, 100mL DMF is added, surpasses
Sound stirring 30min obtains graphene oxide dispersion；
2. the 5A molecular sieve after 9g activation is added in step 1. middle graphene oxide dispersion, dispersion liquid after impregnating for 24 hours
It is filled into three-necked flask；
3. weighing 0.912g methane sulfonyl chloride (methane sulfonyl chloride is 4:1 with graphene oxide molar ratio), 10mL is added
DMF dissolution；
4. under stirring condition, by step 3. obtained in solution be slowly dropped to step 2. obtained in graphene oxide point
In dispersion liquid；
5. step 4. in be transferred in oil bath pan equipped with the three-necked flask of dispersion liquid, connect condenser pipe, biexhaust pipe, lead to nitrogen
20min；
6. weighing 1.616g triethylamine (triethylamine is 8:1 with graphene oxide molar ratio), 10mLDMF dissolution is added；
7. under condition of nitrogen gas, 6. solution that step is obtained is added drop-wise in 5. dispersion liquid that step obtains, 10min is stirred；
8. after completing step 7., disconnecting biexhaust pipe, reaction system closing, condenser pipe connects diaphragm pump, takes out negative pressure
100mbar；
9. opening heating, it is heated to reflux 6h at 80 DEG C, product filters after the reaction was completed, DMF washing, 80 DEG C of vacuum drying
12h, obtain it is hydroxy activated after graphene oxide.
Embodiment 4
1. 0.75g graphene oxide slurry (mass fraction 28%) is added in single-necked flask, 100mL DMF is added, surpasses
Sound stirring 30min obtains graphene oxide dispersion；
2. the 5A molecular sieve after 9g activation is added in step 1. middle graphene oxide dispersion, dispersion liquid after impregnating for 24 hours
It is filled into three-necked flask；
3. weighing 1.19g thionyl chloride (thionyl chloride is 5:1 with graphene oxide molar ratio), it is molten that 10mL DMF is added
Solution；
4. under stirring condition, by step 3. obtained in solution be slowly dropped to step 2. obtained in graphene oxide point
In dispersion liquid；
5. step 4. in be transferred in oil bath pan equipped with the three-necked flask of dispersion liquid, connect condenser pipe, biexhaust pipe, lead to nitrogen
20min；
6. weighing 2.02g triethylamine (triethylamine is 10:1 with graphene oxide molar ratio), 10mLDMF dissolution is added；
7. under condition of nitrogen gas, 6. solution that step is obtained is added drop-wise in 5. dispersion liquid that step obtains, 10min is stirred；
8. after completing step 7., disconnecting biexhaust pipe, reaction system closing, condenser pipe connects diaphragm pump, takes out negative pressure
100mbar；
Heating is opened, is heated to reflux 6h at 80 DEG C, product filters after the reaction was completed, DMF washing, 80 DEG C of vacuum drying 12h,
Obtain it is hydroxy activated after graphene oxide.
Graphene oxide water solution dispersion: 100 parts of graphene oxide water solutions are placed in ultrasonic disperse machine, ultrasonic disperse
40mim。
A kind of activation method of surface of graphene oxide hydroxyl provided by the invention is described in detail above, this
Apply that a specific example illustrates the principle and implementation of the invention in text, the explanation of above example is only intended to
It facilitates the understanding of the method and its core concept of the invention, including best mode, and but also any person skilled in the art
The present invention, including any device or system of manufacture and use can be practiced, and implements the method for any combination.It should be pointed out that
For those skilled in the art, without departing from the principle of the present invention, can also to the present invention into
Row some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.The invention patent is protected
The range of shield is defined by the claims, and may include those skilled in the art it is conceivable that other embodiments.If this
A little other embodiments have the structural element for being not different from claim character express, or if they include wanting with right
Equivalent structural elements of the character express asked without essence difference, then these other embodiments should also be included in the model of claim
In enclosing.
Claims (8)
1. a kind of activation method of graphene oxide, which comprises the following steps:
A after) dispersing graphene oxide in polar solvent, graphene oxide solution is obtained；
B after the graphene oxide solution, activator and the acid binding agent mixing that) obtain above-mentioned steps, reaction system is obtained；
The acid binding agent includes one of triethylamine, pyridine and 4-dimethylaminopyridine or a variety of；
The step B) specifically:
B1) graphene oxide solution for obtaining above-mentioned steps obtains dehydration graphene oxide solution after dehydration；
B2) the dehydration graphene oxide solution that above-mentioned steps obtain is slowly added into the mixed solution of activator and polar solvent
In, after emptying oxygen, obtain intermediate system；
B3) in the absence of oxygen, the mixed liquor of acid binding agent and polar solvent is slowly added into above-mentioned intermediate system, is obtained
Reaction system；
C) in the absence of oxygen, after reaction system heating reaction above-mentioned steps obtained, the graphite oxide after being activated
Alkene；
The step C) specifically:
In the absence of oxygen, in the state that tiny structure is with being heated to reflux, the reaction system that above-mentioned steps are obtained carries out anti-
Ying Hou post-processes the graphene oxide after being activated.
2. activation method according to claim 1, which is characterized in that the polar solvent includes N, N- dimethyl formyl
One of amine, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, tetrahydrofuran, dimethyl sulfoxide and ethylene glycol are a variety of；
The activator includes one of paratoluensulfonyl chloride, trifluoromethanesulfanhydride anhydride, methane sulfonyl chloride and thionyl chloride or more
Kind.
3. activation method according to claim 1, which is characterized in that the matter of the graphene oxide and the polar solvent
Amount volume ratio is (0.1 ~ 2) g:100mL；
The molar ratio of the graphene oxide and the activator is 1:(2 ~ 5)；
The molar ratio of the graphene oxide and the acid binding agent is 1:(4 ~ 10).
4. activation method according to claim 1, which is characterized in that the temperature of the heating reaction is 80 ~ 90 DEG C；
The time of the heating reaction is 4 ~ 10h.
5. activation method according to claim 1, which is characterized in that the dehydration is molecular sieve dehydration processing；
It is described to be incorporated slowly as being added dropwise；
The condition of the anaerobic includes vacuum or is passed through protective gas.
6. activation method according to claim 5, which is characterized in that the step A) in, the graphene oxide includes
Graphene oxide slurry；
The mass fraction of the graphene oxide slurry is 25% ~ 30%；
The mass ratio of the graphene oxide slurry and the molecular sieve is 1:(10 ~ 20).
7. activation method according to claim 1, which is characterized in that the pressure of the tiny structure is 100 ~ 120mbar；
The post-processing step includes one of washing, separation and drying or a variety of；
The temperature of the drying is 50 ~ 60 DEG C；The time of the drying be 12 ~ for 24 hours.
8. a kind of modified graphene oxide, which is characterized in that the activation method as described in claim 1 ~ 7 any one obtained
Graphene oxide after activation, obtains after modified.
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