CN109231186A - Utilize the preparation method of metal ion induction graphene three-dimensional network - Google Patents
Utilize the preparation method of metal ion induction graphene three-dimensional network Download PDFInfo
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- CN109231186A CN109231186A CN201811325260.0A CN201811325260A CN109231186A CN 109231186 A CN109231186 A CN 109231186A CN 201811325260 A CN201811325260 A CN 201811325260A CN 109231186 A CN109231186 A CN 109231186A
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- C01B32/00—Carbon; Compounds thereof
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
Utilize the preparation method of metal ion induction graphene three-dimensional network, it is related to a kind of preparation method of graphene three-dimensional network, graphene three-dimensional network is with graphene oxide or derivatives thereof for initial feed, using metal nanometre cluster, nanogold, metal salt is as auxiliary, in water phase, the system of dissolving each other with rock-steady structure is formed in ethyl alcohol phase or organic phase, and pass through electronation, thermal reduction, solvothermal means, prepare hole intercommunication, size is controllable, the graphene three-dimensional net structure of local order, then by dissolving and rinsing repeatedly, it is regular to obtain hole, the graphene three-dimensional network of stable structure.Graphene three-dimensional net structure can be used for photoelectric functional material, advanced composite material, Ultra-Light Material matrix or reinforcing material, be all with a wide range of applications in fields such as high power power, sewage treatment, effective catalyst, photoelectric detectors.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene three-dimensional network, are induced more particularly to a kind of using metal ion
The preparation method of graphene three-dimensional network.
Background technique
Graphene three-dimensional network is a kind of Ultralight graphene framework material with continuous through-hole structure, in reinforcing material
There is highly important application value with field of functional materials.Primary structure is made of graphene continuous structure and intercommunication hole,
Have the characteristics that lightweight, high intensity, good conductivity, optics Modulatory character.Currently, similar graphene three-dimensional network material (stone
Black alkene foam, graphene aerogel), it is generally prepared using template, freeze-drying correspondingly, former approach can be made
The graphene three-dimensional network of standby structure-controllable out, but usually template can not completely remove, and preparing graphene skeleton need to
A large amount of microsphere template agent are consumed, cost is improved；Later approach can more prepare graphene three-dimensional network at low cost, but
This method there are inefficiency, preparation product there are a large amount of structure randomnesss are strong, the graphene aerogel of preparation has bright
Aobvious hole-closing structure is unfavorable for using as advanced reinforcing material, and the presence of these problems constrains graphene three-dimensional network material
The development of material.Therefore, the ultralight of continuous intercommunication is formed as a three-dimensional structure for regulation graphene is manually made using metal center
Matter graphene three-dimensional net structure to the controllability for realizing the preparation of graphene three-dimensional material and is further implemented its application, is had
Important practical usage.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method using metal ion induction graphene three-dimensional network, the party
Method adjusts the type of metal ion and the graphene three-dimensional network of type functional group's preparation different aperture size, hole controllability
It is good；It is compound to be embedded in different functional particles, can get graphene three-dimensional network composite construction, provides multifunctional platform convenient for application
Change.Optimize for grapheme material performance and prepare light composite material and enhancing skeleton support is provided.
The purpose of the present invention is what is be achieved through the following technical solutions:
Using the preparation method of metal ion induction graphene three-dimensional network, the method is with graphene oxide or graphite oxide
Ene derivative is raw material, using metal ion, metal cluster, metallic nano crystal surface metal ion as metal center, promote
Make graphene oxide or graphene oxide derivative that there is the metal-oxide graphene of topological structure with metal center induced synthesis
Three-dimensional intercommunication network, and by restoring and removing metal, graphene three-dimensional network is made；Including following preparation process:
(1) graphene oxide (or graphene oxide derivative) is passed through into sonic oscillation in decentralized medium, forms stablizing solution,
Its concentration is 0.1 ~ 10mg/mL, and decentralized medium is water, organic solvent and various aprotic solvent；
(2) in graphene oxide (or graphene oxide derivative) stablizing solution, be added surface ionizing metal nanometre cluster,
Metallic nano crystal solution forms semistable metal center-graphene oxide three-dimensional space network structure；
(3) solution system of metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network is carried out same
Step reduction, is prepared containing metal nanometre cluster or nanocrystalline or metal ion graphene three-dimensional net structure；
(4) or by the three-dimensional net structure of alkene containing metallic graphite carbon of preparation metal ion removal is carried out, is removed by dry or solvent,
Finally prepare high purity graphite alkene three-dimensional network.
The preparation method using metal ion induction graphene three-dimensional network, it is described that surface ionizing gold is added
Belong to nano-cluster, metal nanometre cluster, the metal that metallic nano crystal solution is Au, Ag, Cu, Al, Fe, Co, Ni, Zn, Mn transition metal
Nanocrystalline chloride, bromide, iodide, hydroxide solution and sulfuric acid, nitric acid, one of the strong acid solution of cyanic acid and two
It is more than person compound, as manually making a little for metal center.
The preparation method using metal ion induction graphene three-dimensional network, the surface ionizing metal are received
Rice cluster, metallic nano crystal solution concentration are used graphene oxide or graphene oxide derivative) stablizing solution concentration
0.01% ~ 20% mass ratio.
The preparation method using metal ion induction graphene three-dimensional network, the metal center and graphite oxide
The functional group of alkene forms semistable three-dimensional net structure, can be formed by synchronous reduction/drying process, metal ion removal steady
Fixed graphene three-dimensional network.
The advantages and effects of the present invention are:
1. hole controllability of the present invention is good, the type and type functional group for adjusting metal ion can prepare different aperture size
Graphene three-dimensional network.
2. the period of the invention is short, at low cost, this method step is succinct, treatment process is easily realized, does not need complex device i.e.
It can be mass produced.
3. product of the present invention is had excellent performance, graphene three-dimensional network have stable support performance and excellent conduction, every
Hot property.
4. it is compound that the present invention convenient for application and practical, is embedded in different functional particles, graphene three-dimensional network can get
Composite construction provides multifunctional platform convenient for application.
Graphene three-dimensional network prepared by the present invention can be used for special type composite material, aircraft loss of weight, microelectronic device, lithium
Many high-tech sectors such as ion battery, catalyst.
Detailed description of the invention
Fig. 1 is the shape appearance figure of graphene three-dimensional network made from specific embodiment 21.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The graphene three-dimensional net structure that the present invention is obtained using metal ion induction is with graphene oxide or oxidation stone
Black ene derivative is raw material, assists being formed skeleton structure by ion, and by ion exchange and graphite oxide synchronize go back original shape
At graphene three-dimensional network density is 0.001 ~ 0.1gcm3, conductivity 103~105S/m, intensity are 0.1 ~ 10MPa.
The of the invention preparation method using ion auxiliary graphene three-dimensional network is through the following steps that realize: one,
Graphene oxide (or graphene oxide derivative) is formed into stablizing solution, concentration in decentralized medium by sonic oscillation
For 0.1 ~ 10mg/mL, decentralized medium is water, organic solvent and various aprotic solvent.Two, in graphene oxide (or oxygen
Graphite ene derivative) in stablizing solution, surface ionizing metal nanometre cluster, metallic nano crystal solution is added, it is steady to form half
Fixed metal center-graphene oxide three-dimensional space network structure.Three, by graphene oxide (or graphene oxide derivative)-
Metal three dimensional complexes solution synchronizes reduction, prepares the graphene three-dimensional net structure of metal ion.It four, will preparation
The graphene three-dimensional net structure of metal ion carry out ion remaval, removed by dry or solvent, finally prepare stone
Black alkene three-dimensional network.
In preparation method using ion auxiliary graphene three-dimensional network of the invention, graphene oxide described in step 1 is
The graphene oxide that commercially available or laboratory is combined to by chemical oxidation, electrochemistry oxygen.Graphene oxide described in step 1 is derivative
Object is that the structures such as amination, carboxylated, hydroxylating, cyanalation are prepared by modified with functional group such as amino, carboxyl, hydroxyl, cyano
Graphene oxide derivative, detailed process be in graphene oxide be added organic amine, organic acid, Organic Alcohol, silane, boron
Alkane, organic cyanide etc. are modified, and are reacted 1 ~ 5h under reflux conditions, are prepared surface grafting amino, carboxyl, hydroxyl, cyanogen
The graphene oxide derivative of base isoreactivity functional group, concentration range are 0.1 ~ 5mg/mL.
Decentralized medium described in step 1 of the present invention be water, alcohols, ketone, hydro carbons, aprotic solvent (DMF, DMAC, DMSO,
NMP)。
Graphene oxide (or graphene oxide derivative) is passed through into ultrasonic disperse in medium described in step 1 of the present invention,
It can distinguish or independent assortment is added nanoparticle, dispersing agent, stabilizer and carries out compound and stabilize, form stablizing solution as half
Clear solution, suspension.Effect nanoparticle includes: nanogold, semiconductor-quantum-point, polyacid, metallo-organic compound, described
The particle size range of nanoparticle is 1 ~ 50nm.Dispersing agent includes: DMP-30, and stabilizer includes: PVP.
Surface ionizing metal nanometre cluster, metallic nano crystal solution described in step 2 of the present invention, predominantly Fe, Co, Ni,
The metal nanometre cluster of Cu, Zn, Mn transition metal, the chloride of metallic nano crystal, bromide, iodide, hydroxide solution with
And the strong acid solution of sulfuric acid, nitric acid, cyanic acid.
Metal-oxide graphene three-dimensional space chelation structure described in step 2 of the present invention is oxidation centered on metal ion
Graphene (or graphene oxide derivative) functional group is the three-dimensional space self assembly network structure that ligand is formed.
Synchronous restoring method described in step 3 of the present invention be hydrogen reduction, thermal reduction, reducing agent electronation, plasma also
Original, solvothermal, hydrothermal reduction.
The graphene three-dimensional net structure of metal ion described in step 3 of the present invention is Fe, Co, Ni, Cu, Zn, Mn transition
Metal is embedded in the composite construction that graphene three-dimensional network is formed.
Ion remaval method described in step 4 of the present invention is using pickling, solvent cleaning, ultrasonic cleaning mode.
Dry or solvent minimizing technology described in step 4 of the present invention is evaporates, rotarily dries, is dried in vacuo, low temperature is naturally dry
It is dry.
By Step 3: step 4 preparation graphene three-dimensional network, it is light, specific strength is high, good conductivity, hole can
Control.Mechanical strength with higher and structural stability simultaneously.
Embodiment is as follows:
The technical solution of the present invention is not limited to the following list, further includes any between each specific embodiment
Combination.
Specific implementation method one: the present invention uses graphene oxide for raw material, and sonic oscillation is scattered in aqueous solution, and metal is received
Rice cluster is constitution controller, through overstabilization and synchronous reduction, removes metal ion by washing, can be made by electronation
Standby graphene three-dimensional network out.Graphene oxide is commercially available or is made by chemical oxidization method, electrochemical oxidation process.
Specific implementation method two: the difference of this method and method one is to use graphene oxide derivative for raw material, oxygen
Graphite ene derivative is that graphene oxide and organic amine act on the amination graphene oxide derivative to be formed.Other parameters with
Specific embodiment one is identical.
Specific implementation method three: the difference of this method and above method is that using organic acid, as modification, preparation is formed
The graphene oxide derivative of carboxylated.Other parameters are same as the specific embodiment one.
Specific implementation method four: the difference of this method and above method is that using Organic Alcohol, as modification, preparation is formed
Hydroxylated graphene oxide derivative.Other parameters are same as the specific embodiment one.
Specific implementation method five: the difference of this method and above method is that using silane, as modification, preparation forms alkane
The graphene oxide derivative of base.Other parameters are same as the specific embodiment one.
Specific implementation method six: the difference of this method and above method is that using borine, as modification, preparation forms alkane
The graphene oxide derivative of base.Other parameters are same as the specific embodiment one.
Specific implementation method seven: the difference of this method and above method is using organic cyanide as modification, preparation
Form cyanalation graphene oxide derivative.Other parameters are same as the specific embodiment one.
Specific implementation method eight: this method is to prepare using 1 ~ 5h is reacted under counterflow condition with the difference of above method
The graphene oxide derivative of surface grafting functional group, other parameters are same as the specific embodiment one out.
Specific implementation method nine: the difference of this method and above method is to prepare the oxidation stone of surface grafting functional group
Black ene derivative, concentration range are 0.1 ~ 5mg/mL, and other parameters are same as the specific embodiment one.
Specific implementation method ten: present embodiment is to induce graphite using metal ion as described in specific embodiment one
The preparation method of alkene three-dimensional network, through the following steps that realize: one, by graphene oxide (or graphene oxide derivative)
Through ultrasonic disperse in medium, the solution that concentration range is 0.1mg/mL ~ 5mg/mL is formed.Two, in graphene oxide (or oxygen
Graphite ene derivative) in stablizing solution, addition content is 0.0001mg/mL ~ 1mg/mL metal nanometre cluster, nanocrystalline, metal
Solion forms metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network structure.It three, will be golden
Category center-graphene oxide three-dimensional network solution synchronizes electronation, and preparing metal ion is 0.01% ~ 20%
Graphene three-dimensional net structure.Four, the metalliferous graphene three-dimensional net structure of preparation is subjected to washing removal excess metal
Ion removes by dry or solvent, finally prepares the three-dimensional network of alkene containing metallic graphite carbon.
Specific implementation method 11: the difference of this method and above method is to distinguish or nanometer is added in independent assortment
Particle, dispersing agent, stabilizer are carried out compound and are stabilized, and forming stablizing solution is translucent solution, suspension.Act on nanoparticle
Son includes: metal nanometre cluster, nanocrystalline, metallo-organic compound, and the particle size range of the nanoparticle is 1 ~ 50nm.Dispersing agent
It include: DMP-30, stabilizer includes: PVP.Remaining is identical as specific embodiment ten as other parameters.
Specific implementation method 12: the difference of this method and above method is the metal center-graphene oxide to be formed
(or graphene oxide derivative) three-dimensional space be semisteady-state, in the solution stable period be 1 ~ for 24 hours.Remaining and other ginsengs
Number is identical as specific embodiment ten.
Specific implementation method 13: this method is that synchronous chemical reducing agent is sodium borohydride with the difference of above method,
The reducing agents such as potassium borohydride, potassium iodide, reduction temperature are as follows: 80 DEG C ~ 150 DEG C.Remaining and other parameters and specific embodiment ten
It is identical.
Specific implementation method 14: the difference of this method and above method is metal center-graphene oxide is three-dimensional
The solution of network is heat-treated, reduction temperature are as follows: 150 DEG C ~ 450 DEG C.Remaining and other parameters and ten phase of specific embodiment
Together.
Specific implementation method 15: the difference of this method and above method is metal center-graphene oxide is three-dimensional
The solution of network is heat-treated, and reduction needs to carry out under vacuum conditions.Remaining and other parameters and specific embodiment ten
Four is identical.
Specific implementation method 16: the difference of this method and above method is metal center-graphene oxide is three-dimensional
The solution of network is heat-treated, and reduction needs to carry out under inert gas protection.Remaining and other parameters and specific embodiment party
Formula 14 is identical.
Specific implementation method 17: the difference of this method and above method is metal center-graphene oxide is three-dimensional
The solution of network carries out the restoring method that uses of thermal reduction as solvothermal, used medium solvent are as follows: water, ethyl alcohol, acetone, first
The organic solvents such as benzene, aprotic solvent.Remaining is identical as specific embodiment ten as other parameters.
Specific implementation method 18: the difference of this method and above method is solvothermal temperature are as follows: 100 ~ 250
℃.Remaining is identical as specific embodiment 18 as other parameters.
Specific implementation method 19: the difference of this method and above method is metal center-graphene oxide is three-dimensional
The solution of network synchronizes electronation, prepares the metal ion content in graphene three-dimensional net structure are as follows: 1% ~ 5%.
Remaining is identical as specific embodiment 18 as other parameters.
Specific implementation method 20: it is dry that the difference of this method and above method is that the mode for removing solvent can be vacuum
Any one in dry, supercritical drying, natural drying.
Specific embodiment 21: the system of metal ion induction graphene three-dimensional network is utilized described in present embodiment
Preparation Method, through the following steps that realize: one, graphene oxide is passed through into ultrasonic disperse in ethyl alcohol, forms concentration range
For the solution of 1.5mg/mL.Two, in graphene oxide (or graphene oxide derivative) stablizing solution, content, which is added, is
0.015mg/mL copper chloride solution forms metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network
Structure.Three, copper ion center-graphene oxide three-dimensional network solution is synchronized into electronation using potassium borohydride, made
The graphene three-dimensional net structure that standby copper ions out are 1%.Four, the graphene three-dimensional net structure of the cupric of preparation is carried out
Washing removal copper ion removes solvent by dry, finally prepares graphene three-dimensional network.
Table 1 is the performance parameter of graphene three-dimensional network made from specific embodiment 21.
Table 1
| Density | Porosity | Compressive strength | Conductivity |
| 0.03g/cm3 | 95% | 5MPa | 3.5×103S/m |
The graphene three-dimensional network density of this method preparation is 0.03g/cm3, conductivity is 3.5 × 103S/m, compressive strength are
5MPa。
Graphene oxide is commercial product in present embodiment step 1.
Copper chloride solution need to be slowly added into graphene dispersing solution in present embodiment step 2, and stand 8h.
Synchronous chemical reduction procedure needs to carry out in standing solution in present embodiment step 3, reaction time 4h.
Extra copper ion need to can be removed by aqueous cleaning 6 times in present embodiment step 4.
Specific embodiment 22: present embodiment from unlike specific embodiment 21 in step 1 by oxygen
Graphite alkene ultrasonic disperse obtains the graphene oxide solution that concentration is 4mg/mL in ethyl alcohol, and wherein decentralized medium is water.It is other
Step and parameter are identical as specific embodiment 22.
The graphene three-dimensional network density that present embodiment is prepared is 0.05g/cm3。
Embodiment of above is not enumerating for whole embodiments, on this basis the step of replacement, transformation, improve etc.
Realization prepares the technical solution of graphene three-dimensional network, also within scope of the presently claimed invention.
Claims (4)
1. utilizing the preparation method of metal ion induction graphene three-dimensional network, which is characterized in that the method is to aoxidize stone
Black alkene or graphene oxide derivative are raw material, are made using the surface metal ion of metal ion, metal cluster, metallic nano crystal
For metal center, promote graphene oxide or graphene oxide derivative that there is the gold of topological structure with metal center induced synthesis
Category-graphene oxide three-dimensional intercommunication network, and by restoring and removing metal, graphene three-dimensional network is made；Including with
Lower preparation process:
(1) graphene oxide (or graphene oxide derivative) is passed through into sonic oscillation in decentralized medium, forms stablizing solution,
Its concentration is 0.1 ~ 10mg/mL, and decentralized medium is water, organic solvent and various aprotic solvent；
(2) in graphene oxide (or graphene oxide derivative) stablizing solution, be added surface ionizing metal nanometre cluster,
Metallic nano crystal solution forms semistable metal center-graphene oxide three-dimensional space network structure；
(3) solution system of metal center-graphene oxide (or graphene oxide derivative) three-dimensional space network is carried out same
Step reduction, is prepared containing metal nanometre cluster or nanocrystalline or metal ion graphene three-dimensional net structure；
(4) or by the three-dimensional net structure of alkene containing metallic graphite carbon of preparation metal ion removal is carried out, is removed by dry or solvent,
Finally prepare high purity graphite alkene three-dimensional network.
2. the preparation method according to claim 1 using metal ion induction graphene three-dimensional network, which is characterized in that
Surface ionizing metal nanometre cluster, the metallic nano crystal solution of being added is Au, Ag, Cu, Al, Fe, Co, Ni, Zn, Mn transition
The metal nanometre cluster of metal, the chloride of metallic nano crystal, bromide, iodide, hydroxide solution and sulfuric acid, nitric acid,
It is more than one of strong acid solution of cyanic acid and the two compound, as manually making a little for metal center.
3. the preparation method according to claim 1 using metal ion induction graphene three-dimensional network, which is characterized in that
The surface ionizing metal nanometre cluster, metallic nano crystal solution concentration are spread out for institute using graphene oxide or graphene oxide
Biology) stablizing solution concentration 0.01% ~ 20% mass ratio.
4. the preparation method according to claim 1 using metal ion induction graphene three-dimensional network, which is characterized in that
The functional group of the metal center and graphene oxide forms semistable three-dimensional net structure, at synchronous reduction/drying
Reason, metal ion removal can form stable graphene three-dimensional network.
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