CN104261393B - A kind of be reducing agent with guanidine hydrochloride graphene preparation method - Google Patents
A kind of be reducing agent with guanidine hydrochloride graphene preparation method Download PDFInfo
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- CN104261393B CN104261393B CN201410490875.4A CN201410490875A CN104261393B CN 104261393 B CN104261393 B CN 104261393B CN 201410490875 A CN201410490875 A CN 201410490875A CN 104261393 B CN104261393 B CN 104261393B
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Abstract
The present invention to relate to a kind of graphene preparation method being reducing agent with guanidine hydrochloride, and graphene oxide is scattered in water by (1), obtains homodisperse graphene oxide dispersion.(2) soluble high molecular polymers is joined in graphene oxide dispersion, obtain the mixed solution of high molecular polymer and graphene oxide.(3) guanidine hydrochloride is joined in the mixed solution of step (2) gained, the mass ratio of guanidine hydrochloride and graphene oxide is 10:1 ~ 100:1, it is simultaneously introduced alkaline solution and regulates pH to 8 ~ 12, it is placed in oil bath pan stirring reaction, oil bath temperature is 60 ~ 100 DEG C, the stirring reaction time is 1 ~ 5 hour, subsequently by centrifugation, washs and obtain described water-soluble graphene.Preparation technology of the present invention is simple, and equipment requirements is low, it is easy to high-volume prepares Graphene, and the Graphene thus prepared can be used for building sensor and electricity device.
Description
Technical field
The preparation method that the present invention relates to Graphene, the graphene preparation method being particularly reducing agent with guanidine hydrochloride.
Background technology
Graphene is due to the quantum effect of its uniqueness and excellent electricity, calorifics and mechanical property, at following nano electron device and integrated circuit, flexible electronic device, the Novel electronic devices such as ultra-high sensitive senser element, composite, solaode, ultracapacitor, the aspect such as hydrogen storage material is with a wide range of applications.Preparation method about Graphene mainly has physical mechanical stripping means, vapour deposition process and chemical method etc..Mechanical means includes micromechanics stripping means, the method for epitaxial growth method and heating SiC.Such as, Novoselov et al. reports in Science (2004,306:666-669) and adopts the method that graphite peeled off by micromechanics to prepare single crystal graphene thin film, it is possible to stable existence under external environment, and has metallicity.But, this method be utilize friction graphite surface obtain thin slice to filter out the graphene platelet of monolayer, its size is wayward, it is impossible to the graphite flake that reliably factory length is enough.C.Berger et al. is at JournalofPhysicsChemistry (2004, in 108:19912-19916), report is by heating monocrystal SiC elimination Si, monocrystalline (0001) face decomposites graphene sheet layer, thus controllably preparing single or multiple lift Graphene.But, in preparation process, the Graphene thickness of gained is generally determined by heating-up temperature, and preparation large area has the Graphene of single thickness and just becomes relatively difficult.
Relative to physical method, chemical method is prepared Graphene and is had productivity height, and preparation method is simple, less costly and the advantage that can be mass-produced, and therefore, the method has become common method prepared by Graphene.Wherein, adopt the method for chemical method redox graphene to prepare Graphene and start research boom prepared by Graphene.At present, in the process that graphene oxide is reduced, the reducing agent of selection mainly has hydration hydrazine and its derivative, NaBH4, p-phenylenediamine, sulfur-containing compound etc., major part reducing agent is poisonous and volatile, is unfavorable for large-scale production.Although, Guo Shouwu et al. and J.I.Paredes et al. is at chemcommun (2010,46:1112-1114) and JPhysChemC (2010,114:6426 6432) middle report: VitaminC is an effective reducing agent, its reducing power can compared with hydrazine, but VitaminC price comparison is high, limits the large-scale production of Graphene.Therefore, develop simple, efficient, low cost and eco-friendly method and reducing agent is very important.
Summary of the invention
The technical problem to be solved in the present invention is to provide the graphene preparation method being reducing agent with guanidine hydrochloride that a kind of method is simple, cost is low.
For solving above technical problem, provided by the invention a kind of be reducing agent with guanidine hydrochloride graphene preparation method, comprise the following steps:
(1) graphene oxide is scattered in water, obtains homodisperse graphene oxide dispersion.
(2) soluble high molecular polymers is joined in graphene oxide dispersion, obtain the mixed solution of high molecular polymer and graphene oxide.
(3) guanidine hydrochloride is joined in the mixed solution of step (2) gained, the mass ratio of guanidine hydrochloride and graphene oxide is 10:1 ~ 100:1, it is simultaneously introduced alkaline solution and regulates pH to 8 ~ 12, it is placed in oil bath pan stirring reaction, oil bath temperature is 60 ~ 100 DEG C, the stirring reaction time is 1 ~ 5 hour, subsequently by centrifugation, washs and obtain described water-soluble graphene.
As preferred scheme, in step (1), graphite oxide is joined in redistilled water, process 20 ~ 90 minutes with cell crushing instrument, continue supersound process 10 ~ 60 minutes with ultrasound wave subsequently, obtain homodisperse graphene oxide dispersion.In this step processing procedure, greatly limit, with short period ground, bulk graphene oxide can be peeled off into single or multiple lift through the break process of 20 ~ 90 minutes；Then pass through the supersound process of 10 ~ 60 minutes, further the graphite oxide of multilamellar or bilayer is peeled off into monolayer, substantially increase the specific surface area of graphene oxide, be conducive to exposing reaction site, the process of Accelerating reduction reaction.
As preferred scheme, the concentration of graphene oxide dispersion is preferably 0.1 ~ 10mg/mL, and concentration continues increase can further enhance the auto polymerization trend of graphene oxide, reduces its dispersibility in a solvent.
As preferred scheme, in step (2), being joined by soluble high molecular polymers in graphene oxide dispersion, ultrasonic disperse obtains the mixed solution of high molecular polymer and graphene oxide after 5 ~ 30 minutes.In this processing procedure, the existence of soluble high molecular polymers, it is possible to interacted by the oxy radical of intermolecular force with surface of graphene oxide and edge, be conducive to strengthening stability and the water solublity of graphene oxide.
As preferred scheme, soluble high molecular polymers one in polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, Polyethylene Glycol, hydroxymethyl cellulose, polyacrylic acid.
As preferred scheme, soluble high molecular polymers mass concentration in mixed solution is 0.01 ~ 0.1mg/mL, and the concentration of soluble high molecular polymers continues increase can increase the viscosity of solution, is unfavorable for further reduction subsequently on the contrary.
As preferred scheme, alkaline solution added in step (3) is selected from the KOH solution of the ammonia of mass percentage concentration 10% ~ 28%, the NaOH solution of 0.1 ~ 5mol/L, 0.1 ~ 5mol/L.Range for 8 ~ 12 by regulating pH value of solution, be conducive to the hydrolysis of guanidine hydrochloride, play its reducing power to greatest extent.
Preparation technology of the present invention is simple, and equipment requirements is low, it is easy to high-volume prepares Graphene；The existence of soluble high molecular polymers substantially improves the water solublity of Graphene, is simultaneously also beneficial to the further preparation of graphene film.Adopt guanidine hydrochloride as reducing agent, prepare can the Graphene of stable dispersion in aqueous, the Graphene thus prepared can be used for building sensor and electricity device.
Accompanying drawing explanation
Fig. 1 is step schematic diagram of the present invention.
Fig. 2 is the ultraviolet-visible spectrogram of graphene oxide and gained Graphene in embodiment 1.
Fig. 3 is the transmission electron microscope photo of the Graphene prepared by embodiment 2.
Detailed description of the invention
Below in conjunction with drawings and Examples, claimed technical scheme is done explanation clear, complete further.
Embodiment 1
(1) preparation of graphene oxide: at room temperature, adds the graininess native graphite 2g, sodium nitrate 1g of 500 orders in 250mL there-necked flask and is cooled to 0 DEG C；Then, 50mL concentrated sulphuric acid is added in there-necked flask and is sufficiently stirred for 30 minutes, and keep the temperature of reaction system not higher than 10 DEG C；In 1 hour, then 7 grams of potassium permanganate divide 3 batches add in there-necked flask, keep temperature of reaction system not higher than 20 DEG C.Finally withdraw cryostat, with water-bath, temperature of reaction system is heated to 35 ± 3 DEG C, be sufficiently stirred for 2 hours, obtain brown graphite suspension.Being slowly added in there-necked flask by 90mL deionized water, system temperature is increased to 70 DEG C suddenly, and generates with a large amount of gases, and the suspension of dilution reacts 15 minutes at this temperature；Then in there-necked flask, add the aqueous hydrogen peroxide solution 7mL that mass percent concentration the is 30% and deionized water 55mL that temperature is 40 DEG C, obtain glassy yellow graphite oxide dispersion.By suspension filtered while hot, obtain yellowish-brown filter cake.With 150mL dilute hydrochloric acid (3wt%), 45 DEG C, after Cake Wash 3 times, it is scattered in 600mL water, is centrifuged 20 minutes through 4000rpm, the gel graphite oxide obtained is transferred to 40 DEG C of vacuum drying oven, dry and obtain graphene oxide in 24 hours.
(2) 15mg graphene oxide is joined in 100mL redistilled water, process 40 minutes with cell crushing instrument, then with ultrasonic echography 30 minutes, obtain the graphene oxide dispersion that concentration is 0.15mg/mL.
(3) 2mg polyvinylpyrrolidone is joined in the graphene oxide dispersion of (2) gained, ultrasonic 10 minutes, obtain the mixed solution of polyvinylpyrrolidone and graphene oxide.
(4) 180mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, be subsequently adding the ammonia of 25%, regulate pH value of solution to 9.0, it is placed in 80 DEG C of oil bath pans, stirring reaction 3 hours, is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene (Fig. 2 shows ultraviolet-visible spectrogram).
Embodiment 2
(1) preparation of graphene oxide is with embodiment 1.
(2) 20mg graphene oxide is joined in 50mL redistilled water, process 50 minutes with cell crushing instrument, then with ultrasonic echography 40 minutes, obtain the graphene oxide dispersion that concentration is 0.4mg/mL.
(3) 3mg polyacrylamide is joined in the graphene oxide dispersion of (2) gained, ultrasonic 15 minutes, obtain the mixed solution of polyacrylamide and graphene oxide.
(4) 300mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, it is subsequently adding the NaOH solution of 1mol/L, regulate pH value of solution to 9.0, it is placed in 90 DEG C of oil bath pans, stirring reaction 2.5 hours, it is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene (Fig. 3 shows projection electromicroscopic photograph).
Embodiment 3
(1) preparation of graphene oxide is with embodiment 1.
(2) 50mg graphene oxide is joined in 100mL redistilled water, process 90 minutes with cell crushing instrument, then with ultrasonic echography 60 minutes, obtain the graphene oxide dispersion that concentration is 0.5mg/mL.
(3) 5mg Polyethylene Glycol is joined in the graphene oxide dispersion of (2) gained, ultrasonic 30 minutes, obtain the mixed solution of polyacrylamide and graphene oxide.
(4) 700mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, be subsequently adding the NaOH solution of 2mol/L, regulate pH value of solution to 11.0, be placed in 90 DEG C of oil bath pans, stirring reaction 4 hours, it is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene.
Embodiment 4
(1) preparation of graphene oxide is with embodiment 1.
(2) 10mg graphene oxide is joined in 100mL redistilled water, process 20 minutes with cell crushing instrument, then with ultrasonic echography 10 minutes, obtain the graphene oxide dispersion that concentration is 0.1mg/mL.
(3) 1mg polyvinyl alcohol is joined in the graphene oxide dispersion of (2) gained, ultrasonic 5 minutes, obtain the mixed solution of polyvinyl alcohol and graphene oxide.
(4) 1000mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, be subsequently adding the KOH solution of 0.1mol/L, regulate pH value of solution to 8.0, it is placed in 60 DEG C of oil bath pans, stirring reaction 1 hour, is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene.
Embodiment 5
(1) preparation of graphene oxide is with embodiment 1.
(2) 100mg graphene oxide is joined in 100mL redistilled water, process 60 minutes with cell crushing instrument, then with ultrasonic echography 20 minutes, obtain the graphene oxide dispersion that concentration is 1.0mg/mL.
(3) 10mg hydroxymethyl cellulose is joined in the graphene oxide dispersion of (2) gained, ultrasonic 20 minutes, obtain the mixed solution of hydroxymethyl cellulose and graphene oxide.
(4) 1000mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, be subsequently adding the NaOH solution of 5mol/L, regulate pH value of solution to 12.0, it is placed in 100 DEG C of oil bath pans, stirring reaction 5 hours, is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene.
Embodiment 6
(1) preparation of graphene oxide is with embodiment 1.
(2) 1000mg graphene oxide is joined in 100mL redistilled water, process 70 minutes with cell crushing instrument, then with ultrasonic echography 30 minutes, obtain the graphene oxide dispersion that concentration is 10mg/mL.
(3) 8mg polyacrylic acid is joined in the graphene oxide dispersion of (2) gained, ultrasonic 15 minutes, obtain the mixed solution of polyacrylic acid and graphene oxide.
(4) 12000mg guanidine hydrochloride is joined in the mixed liquor of (3) gained, be subsequently adding 10% ammonia spirit (or 28% ammonia spirit), regulate pH value of solution to 10.0, it is placed in 70 DEG C of oil bath pans, stirring reaction 4 hours, is centrifuged with redistilled water, washs 3 times, obtain water-soluble graphene.
Claims (8)
1. the graphene preparation method that a kind is reducing agent with guanidine hydrochloride, it is characterised in that comprise the following steps:
(1) graphene oxide is scattered in water, obtains homodisperse graphene oxide dispersion；
(2) soluble high molecular polymers is joined in graphene oxide dispersion, obtain the mixed solution of high molecular polymer and graphene oxide；
(3) guanidine hydrochloride is joined in the mixed solution of step (2) gained, the mass ratio of guanidine hydrochloride and graphene oxide is 10:1 ~ 100:1, it is simultaneously introduced alkaline solution and regulates pH to 8 ~ 12, it is placed in oil bath pan stirring reaction, oil bath temperature is 60 ~ 100 DEG C, the stirring reaction time is 1 ~ 5 hour, subsequently by centrifugation, washs and obtain described Graphene.
2. method according to claim 1, it is characterized in that: in step (1), add graphene oxide in redistilled water, process 20 ~ 90 minutes with cell crushing instrument, continue supersound process 10 ~ 60 minutes with ultrasound wave subsequently, obtain homodisperse graphene oxide dispersion.
3. method according to claim 1 and 2, it is characterised in that: the concentration of graphene oxide dispersion is preferably 0.1 ~ 10mg/mL.
4. method according to claim 1, it is characterised in that: in step (2), being joined by soluble high molecular polymers in graphene oxide dispersion, ultrasonic disperse obtains the mixed solution of high molecular polymer and graphene oxide after 5 ~ 30 minutes.
5. the method according to claim 1 or 4, it is characterised in that: soluble high molecular polymers one in polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, Polyethylene Glycol, hydroxymethyl cellulose, polyacrylic acid.
6. the method according to claim 1 or 4, it is characterised in that: soluble high molecular polymers mass concentration in mixed solution is 0.01 ~ 0.1mg/mL.
7. method according to claim 5, it is characterised in that: soluble high molecular polymers mass concentration in mixed solution is 0.01 ~ 0.1mg/mL.
8. method according to claim 1, it is characterised in that: alkaline solution added in step (3) is selected from the KOH solution of the ammonia of mass percentage concentration 10% ~ 28%, the NaOH solution of 0.1 ~ 5mol/L, 0.1 ~ 5mol/L.
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