CN103183340B - A kind of graphene oxide film of ultra high modulus and high intensity and preparation method thereof - Google Patents
A kind of graphene oxide film of ultra high modulus and high intensity and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to nano-functional material technical field, relate to graphene oxide film of a kind of ultra high modulus and high intensity and preparation method thereof, at least prepared by following three kinds of raw materials: graphene oxide, containing catechol structure inorganic agent, cross-linking agent, it is possible to containing other components.The feature of this graphene oxide film is sized macroscopic, and has ultra high modulus and high intensity.Wherein graphene oxide raw material is to utilize modified Hummers method to prepare, and inorganic agent is the small-molecule substance that dopamine etc. has catechol structure, and cross-linking agent is the material that Polyetherimide etc. has many reactive groups.The advantage of the method is that graphene oxide is cheap and easy to get, has biocompatibility, gained enhanced film excellent in mechanical performance, has wide practical use at aspects such as packaging, separation, ultracapacitor, conduction, heat conduction.
Description
Technical field
The invention belongs to nano-functional material technical field, the graphene oxide relating to a kind of ultra high modulus and high intensity is thin
Film and preparation method thereof, is at least prepared by following three kinds of raw materials: graphene oxide, containing catechol structure inorganic agent, crosslinking
Agent, it is possible to containing other components.The feature of this graphene oxide film is sized macroscopic, and has ultra high modulus and high-strength
Degree.
Background technology
Thin-film material is the part that modern science and technology is indispensable, is widely used in separation, electronic apparatus and micro-nano electronics
The fields such as device, protective layer and adhesion layer.Inorganic thin film material based on nano components successful commercialization is applied, and mainly should
For aspects such as high-temperature adhesives, protective layer, high heat-conductivity conductings, as peeled off the thin film of piezoid.
Graphene oxide (Graphene Oxide) is a kind of monolayer carbon atom two-dimensional material containing multiple oxy radical,
By sp2A large amount of oxy radicals (hydroxyl, carboxyl, epoxy radicals etc.) group on hydbridized carbon atoms conjugate planes and surface thereof and edge
Becoming, it has the specific surface area of super large and excellent mechanical property, in polymer composites, electromagnetism device, biological medicine
Etc. aspect be widely used.
The graphite oxide that graphene oxide is mainly obtained by strong acid graphite oxide, graphite layers in graphite oxide
Increase to 7 ~ 10 away from by 3.35 before aoxidizing, and show as hydrophilic, heated or ultrasonic stripping in water, it is easy to
Form the graphene oxide lamellar structure separated.
The graphene oxide sheet of monolayer has extremely large Young's modulus (200-500 GPa) and fracture strength (63
GPa), but, the size limitation of its Nano grade it as the application of macroscopic material.Recent study finds, graphite oxide
Alkene can be by simple sucking filtration or the graphene oxide film being self-assembly of macroscopic view at gas-liquid interface.Due to graphene oxide
The hydrogen bond action of sheet interlayer, pure graphene oxide film itself has certain mechanical property.But, current document is reported
Various graphene oxide films, Young's modulus is generally at 6-42 GPa, and hot strength is at 76-293 MPa, well below monolayer
Graphene oxide sheet, it is impossible to embody its performance advantage.Therefore, graphene oxide film is strengthened by chemically or physically method
Mechanical property be a kind of suitable, effective manner.
Summary of the invention
The present invention relates to graphene oxide film of a kind of ultra high modulus and high intensity and preparation method thereof, at least by following
Three kinds of raw materials prepare: graphene oxide, containing catechol structure inorganic agent, cross-linking agent, it is possible to containing other components.This oxidation
The feature of graphene film is sized macroscopic, and has ultra high modulus and high intensity.Graphite oxide used in the present invention
Alkene, is from expanded graphite, utilizes modified Hummers method oxidation to prepare gained, it is also possible to be to utilize other method such as
Graphite oxide prepared by Brodie method, Staudenmaier method, Hummers method and the various methods improved on this basis
Alkene.
In the present invention containing catechol structure inorganic agent, for having the catechol small molecule derivative of adjacent diphenol structure, tool
Body is the derivant of the hydrochlorate of dopamine, epinephrine, chlorogenic acid or above-mentioned substance.Catechol structure in the basic conditions by
Dioxygen oxidation in air becomes quinoid structure, and meanwhile, benzene ring structure forms free radical, is concurrently conigenous poly-, is coated on graphite oxide
Alkene surface, after acidity is washed, quinoid structure becomes catechol structure again.
Cross-linking agent used in the present invention, for molecular weight be 500-50000 there is polyamino oligomer cross-linking agent, tool
Body is polyetherimide oligomer, polypropylene amine oligomer etc..Catechol structure is oxidized to quinoid structure in the basic conditions,
Easily with amino generation Michael addition or schiff base reaction, thus form chemical bond cross-linked structure, play potentiation.
In the material of the present invention, also can use other auxiliary agent various, such as pH buffer agent, oxidant, reducing agent etc., not affect
The performance of institute's invention material, and use according to practical situation.In the present invention several Main Components composition (mass parts) ratio by
Dispersibility and the mechanical strength of graphene oxide film after graphene oxide process determine.
The mass fraction ratio of graphene oxide, catechol structure class inorganic agent and cross-linking agent is as follows:
Graphene oxide 100 parts,
Containing catechol structure inorganic agent 0.01-100 part,
Cross-linking agent 0.01-200 part.
In preparation method, there are following steps:
(1) expanded graphite is made dispersion graphene oxide；Expanded graphite utilize modified Hummers method oxidation prepare
Graphene oxide, takes a certain amount of graphene oxide (GO) and is placed in the trishydroxymethylaminomethane (Tris, 10mM) of pH8.5 and buffers molten
Ultrasonic disperse 30 minutes in liquid, obtain stable dispersion.
(2) graphene oxide is processed with containing catechol structure inorganic agent dispersion；Ice-water bath adds and ties containing catechol
Structure inorganic agent, dissolves for ultrasonic 10 minutes, then transposition magnetic agitation 24h, sucking filtration, is first washed to neutrality with pickling again, is placed in 25 DEG C
Vacuum drying oven is dried the graphene oxide (PGO) obtained through processing containing catechol structure inorganic agent.
(3) graphene oxide (PGO) through processing containing catechol structure inorganic agent and the cross-linking agent that step (2) are obtained exist
PH neutral buffer solution mixes；Take a certain amount of PGO phosphate (PBS, the 0.2M Na at pH7.02HPO4 / 0.2M
NaH2PO4=19/31) ultrasonic disperse 1h in buffer solution, obtains stable dispersion.Add pH7.0 dissolved with polyetherimide
The PBS buffer solution of amine (Polyetherimide, PEI, molecular weight 600), ultrasonic mixing 1h, sucking filtration obtains uncrosslinked
PGO+PEI composite membrane.
(4) the PGO+PEI composite membrane obtained in step (3) is cross-linked under basic buffer conditions the oxidation of prepared enhancing
Graphene film；Composite membrane is placed in the Tris buffer solution of pH8.5, makes PEI hand over the inorganic agent containing catechol structure
Connection, obtains the graphene oxide film strengthened.
Detailed description of the invention
The present invention is further elaborated by the following examples, wherein forms number, content is by weight.
Embodiment 1
100 parts of graphene oxides (GO) are placed in trishydroxymethylaminomethane (Tris, the 10mM) buffer solution of pH8.5
Ultrasonic 30 minutes, it is configured to the stable dispersion system that concentration is 0.5 mg/mL.50 parts of dopamine hydrochlorides are added in ice-water bath,
Within ultrasonic 10 minutes, dissolve, then transposition magnetic agitation 24h, sucking filtration, first it is washed to neutrality with pickling again, is placed in 25 DEG C of vacuum drying ovens and does
The graphene oxide (PGO) that dry acquisition dopamine processes.Take 92.5 parts of PGO phosphate (PBS, 0.2M Na at pH7.02HPO4
/ 0.2M NaH2PO4=19/31) ultrasonic disperse 1h in buffer solution, obtains stable dispersion.Add pH7.0 dissolved with
The PBS buffer solution of 7.5 parts of Polyetherimide (Polyetherimide, PEI, molecular weight 600), ultrasonic mixing 1h, sucking filtration obtains
To uncrosslinked PGO+PEI composite membrane.Composite membrane is placed in the Tris buffer solution of pH8.5 immersion 30 minutes, makes PEI with poly-
Dopamine crosslinks, and obtains the graphene oxide film strengthened.Thin film is cut into rectangular specimen and carries out extension test, relatively
In pure graphene oxide sucking filtration thin film, the modulus of this enhanced film and intensity have been respectively increased 159.5% and 44.9%.
Embodiment 2
Other are with embodiment 1, and the ratio of GO and dopamine inorganic agent changes 100 parts and 80 parts into, and it is thin that final crosslinking obtains
Film is relative to pure graphene oxide sucking filtration thin film, and modulus and intensity have been respectively increased 202% and 35%.
Embodiment 3
Other are with embodiment 1, and the ratio of PGO and PEI changes 85 parts and 15 parts into, thin relative to pure graphene oxide sucking filtration
Film, the modulus of this enhanced film and intensity have been respectively increased 297.7% and 50.8%.
Embodiment 4
Other are with embodiment 1, and the ratio of PGO and PEI changes 70 parts and 30 parts into, thin relative to pure graphene oxide sucking filtration
Film, the modulus of this enhanced film and intensity have been respectively increased 437% and 83.5%.
Embodiment 5
Other are with embodiment 1, and the ratio of PGO and PEI changes 55 parts and 45 parts into, thin relative to pure graphene oxide sucking filtration
Film, the modulus of this enhanced film and intensity have been respectively increased 373.9% and 73.8%.
Embodiment 6
Being placed in by 100 parts of GO in the Tris buffer solution of pH8.5 ultrasonic 30 minutes, being configured to solubility is 0.5 mg/mL's
Stable dispersion system.In ice-water bath, add 50 parts of dopamine hydrochlorides, within ultrasonic 10 minutes, dissolve, then transposition magnetic agitation 24h, take out
Filter, first pickling is washed to neutrality again, is placed in 25 DEG C of vacuum drying ovens and is dried acquisition PGO.Take 70 parts of PGO and buffer molten at the PBS of pH7.0
Ultrasonic disperse 1h in liquid, obtains stable dispersion.Add the pH7.0 PBS buffer solution dissolved with 30 parts of PEI, ultrasonic mixing
1h, sucking filtration obtains uncrosslinked PGO+PEI composite membrane.The Tris buffer solution adding appropriate pH8.5 carries out sucking filtration, necessarily
Outer pressure makes PEI crosslink with dopamine, obtains the graphene oxide film of super enhancing.Extension test result shows, relatively
In pure graphene oxide sucking filtration thin film, the modulus of this enhanced film and intensity have been respectively increased 554% and 115%.
Embodiment 7
Being placed in by 100 parts of GO in the Tris buffer solution of pH8.5 ultrasonic 30 minutes, being configured to solubility is 0.5 mg/mL's
Stable dispersion system.In ice-water bath, add 50 parts of dopamine hydrochlorides, within ultrasonic 10 minutes, dissolve, then transposition magnetic agitation 24h, take out
Filter, first pickling is washed to neutrality again, is placed in 25 DEG C of vacuum drying ovens and is dried acquisition PGO.Take 100 parts of PGO to buffer at the PBS of pH7.0
Ultrasonic disperse 1h in solution, obtains stable dispersion, and sucking filtration obtains PGO composite membrane.Extension test result shows, relative to
Pure graphene oxide sucking filtration thin film, the modulus of PGO composite membrane and intensity have been respectively increased 93.7% and 19.6%.
Embodiment 8
Being placed in by 100 parts of GO in the Tris buffer solution of pH8.5 ultrasonic 30 minutes, being configured to solubility is 0.5 mg/mL's
Stable dispersion system.In ice-water bath, add 50 parts of dopamine hydrochlorides, within ultrasonic 10 minutes, dissolve, then transposition magnetic agitation 24h, take out
Filter, first pickling is washed to neutrality again, is placed in 25 DEG C of vacuum drying ovens and is dried acquisition PGO.Take 92.5 parts of PGO to buffer at the PBS of pH7.0
Ultrasonic disperse 1h in solution, obtains stable dispersion.Add the pH7.0 PBS buffer solution dissolved with 7.5 parts of PEI, ultrasonic mixed
Closing 1h, sucking filtration obtains uncrosslinked PGO+PEI composite membrane.Extension test result shows, relative to pure graphene oxide sucking filtration
Thin film, the modulus of this uncrosslinked PGO+PEI composite membrane and intensity have been respectively increased 94% and 19.5%.
Embodiment 9
Other are with embodiment 8, and the ratio of PGO and PEI changes 85 parts and 15 parts into, thin relative to pure graphene oxide sucking filtration
Film, the modulus of this uncrosslinked PGO+PEI composite membrane and intensity have been respectively increased 93.4% and 19.1%.
Embodiment 10
Other are with embodiment 8, and the ratio of PGO and PEI changes 77.5 parts and 22.5 parts into, takes out relative to pure graphene oxide
Filter thin film, the modulus of this uncrosslinked PGO+PEI composite membrane and intensity have been respectively increased 93.4% and 19.5%.
Embodiment 11
Other are with embodiment 1, and the inorganic agent of graphene oxide used is chlorogenic acid.Finally cross-link the thin film that obtains relative to
Pure graphene oxide sucking filtration thin film, modulus and intensity have been respectively increased 325.5% and 40.6%.
Embodiment 12
Other are with embodiment 1, and the inorganic agent of graphene oxide used is epinephrine.Finally cross-link the thin film obtained relative
In pure graphene oxide sucking filtration thin film, modulus and intensity have been respectively increased 300.5% and 50.6%.
Embodiment 13
Other are with embodiment 1, and cross-linking agent used is that (Polyallylamine, PAA, molecular weight is about for polypropylene amine oligomer
3000).Finally cross-linking the thin film obtained relative to pure graphene oxide sucking filtration thin film, modulus and intensity are respectively increased
393.8% and 75.1%.
The modulus of the various graphene oxide film of table 1 and intensity
Claims (4)
1. there is a graphene oxide film for ultra high modulus and intensity, this graphene oxide film sized macroscopic, and have
Ultra high modulus and high intensity, it is characterised in that this graphene oxide film at least includes following three kinds of compositions: graphene oxide, contain
Catechol structure surface conditioning agent and cross-linking agent, optionally containing other auxiliary agent,
Wherein, graphene oxide, mass fraction ratio containing catechol structure surface conditioning agent and cross-linking agent are as follows:
Graphene oxide 100 parts,
Containing catechol structure surface conditioning agent 50 parts,
Cross-linking agent 0.01-200 part；
The described surface conditioning agent containing catechol structure is specially epinephrine or chlorogenic acid；
Described cross-linking agent is specially Polyetherimide (PEI)；
The preparation method of above-mentioned graphene oxide film, specifically comprises the following steps that
(1) expanded graphite is made dispersion graphene oxide；
(2) graphene oxide is processed with containing catechol structure surface conditioning agent dispersion；
(3) graphene oxide (PGO) through processing containing catechol structure surface conditioning agent dispersion step (2) obtained and crosslinking
Agent mixes in pH neutral buffer solution, obtains uncrosslinked PGO+PEI composite membrane；
(4) the PGO+PEI composite membrane obtained in step (3) is cross-linked under basic buffer conditions the graphite oxide of prepared enhancing
Alkene thin film.
Graphene oxide film the most according to claim 1, it is characterised in that described graphene oxide is for graphite to be
Raw material, utilizes Brodie method, Staudenmaier method or Hummers method and the various methods that improve on this basis to prepare
Graphene oxide, or the graphene oxide of various degree of oxidations prepared by other any means.
Graphene oxide film the most according to claim 1, it is characterised in that other described auxiliary agent, for pH buffer agent,
Oxidant or reducing agent.
4. having a preparation method for the graphene oxide film of ultra high modulus and intensity as claimed in claim 1, it is special
Levy and be that preparation method is as follows:
(1) expanded graphite is made dispersion graphene oxide；
(2) graphene oxide is processed with containing catechol structure surface conditioning agent dispersion；
(3) graphene oxide (PGO) through processing containing catechol structure surface conditioning agent dispersion step (2) obtained and crosslinking
Agent mixes in pH neutral buffer solution, obtains uncrosslinked PGO+PEI composite membrane；
(4) the PGO+PEI composite membrane obtained in step (3) is cross-linked under basic buffer conditions the graphite oxide of prepared enhancing
Alkene thin film.
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| CN103407997B (en) * | 2013-07-19 | 2016-04-20 | 北京航空航天大学 | A kind of preparation in macroscopic quantity method that can be used for the macroscopic three dimensional graphene aerogel sorbing material of indoor air purification |
| CN103464013B (en) * | 2013-07-25 | 2014-11-05 | 烟台绿水赋膜材料有限公司 | High-performance hybrid separation membrane and preparation method thereof |
| CN103480278B (en) * | 2013-09-06 | 2015-02-25 | 烟台绿水赋膜材料有限公司 | Preparation method and application of anti-pollution hydrophilic separating membrane |
| CN103882442B (en) * | 2014-04-16 | 2015-09-30 | 武汉科技大学 | A kind of stainless steel surface three-dimensional manometer C film and preparation method thereof |
| CN104525107A (en) * | 2014-12-03 | 2015-04-22 | 杜茂龙 | Graphene-based haze-resisting mask filtering material and preparation method thereof |
| CN104695250B (en) * | 2015-03-05 | 2016-05-25 | 苏州经贸职业技术学院 | A kind of polyphenol fabric-modifying agent and preparation method thereof |
| KR102370097B1 (en) * | 2017-03-29 | 2022-03-04 | 삼성전기주식회사 | Electronic Component and System in Package |
| CN107051229A (en) * | 2017-04-17 | 2017-08-18 | 江苏大学 | A kind of preparation method and its usage of graphene oxide/titanium dioxide stratiform composite membrane of polyethyleneimine crosslinking |
| CN109956469B (en) * | 2017-12-26 | 2020-08-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Enzymatic degradation method of three-dimensional graphene and application thereof |
| CN111318172B (en) * | 2018-12-17 | 2022-01-25 | 中国石油化工股份有限公司 | Preparation method of polymer-modified graphene filtering membrane |
| CN109627004B (en) * | 2018-12-19 | 2022-01-07 | 重庆大学 | Heat-conducting and electric-conducting graphene film and preparation method thereof |
| CN111437737B (en) * | 2020-04-10 | 2021-08-06 | 江南大学 | Hydrophilic self-cleaning oil-water separation membrane and preparation method thereof |
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| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
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| 多巴胺的自聚-附着行为与膜表面功能化;徐又一等;《膜科学与技术》;20110630;第31卷(第3期);第32页-第38页 * |
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