CN101634032A - Green and fast electrochemical preparation method for graphene - Google Patents
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- CN101634032A CN101634032A CN200910184202A CN200910184202A CN101634032A CN 101634032 A CN101634032 A CN 101634032A CN 200910184202 A CN200910184202 A CN 200910184202A CN 200910184202 A CN200910184202 A CN 200910184202A CN 101634032 A CN101634032 A CN 101634032A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
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- 229910045601 alloy Inorganic materials 0.000 claims description 11
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
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- GZCWLCBFPRFLKL-UHFFFAOYSA-N 1-prop-2-ynoxypropan-2-ol Chemical compound CC(O)COCC#C GZCWLCBFPRFLKL-UHFFFAOYSA-N 0.000 description 1
- 102000013563 Acid Phosphatase Human genes 0.000 description 1
- 108010051457 Acid Phosphatase Proteins 0.000 description 1
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- 239000002064 nanoplatelet Substances 0.000 description 1
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Abstract
The invention relates to an electrochemical preparation method for graphene, comprising the following steps: taking chemical and electrochemical stability metal and alloy or nonmetal conductor materials as a cathode and an anode, under the condition of stirring, the temperature of 5 below zero DEG C to 90 DEG C and a constant voltage of negative 1.5 V to 10.0negative V, electrolytic reduction is carried out on oxidation state graphene solution for 1min to 10h, to form high-quality graphene on the surface of a cathode electrode; or coating the oxidation state graphene solution on the surface of cathode materials in a dripping way to obtain the grapheme by reducing, and the grapheme is used for applications of modifying the electrode as biosense, and the like. In the method for preparing the graphene, an oxygen-containing functional group on oxidation state graphene is utilized to be reduced by obtaining electrons on the cathode. Except needing one electrochemical workstation, the invention does not need any other special equipment, therefore, the invention has simple manufacture method, easy control of a reaction process, low cost, no pollution, high quality of the prepared graphene, and easy popularization and use of the preparation technology.
Description
Technical field
The present invention relates to a kind of preparation method of graphene, this method be a kind of utilize electrochemical techniques prepare Graphene green novel method fast.
Background technology
Graphene is a kind of two dimensional crystal that is the carbon atom individual layer of honeycomb fashion hexagonal array.Because Graphene has excellent electricity, calorifics and mechanical property, be expected in the acquisition widespread use of fields such as high-performance nanometer electronic device, transmitter, nano composite material, battery and ultracapacitor, field emmision material.Therefore, the Graphene that just occurred in 2004 becomes physics, chemistry and materialogy hot research in recent years rapidly.
Referring to:
1?Katsnelson，M.I.Graphene：Carbon?in?Two?Dimensions.Mater.Today?2007，10，20-27.
2?Avouris，P.；Chen，Z.；Perebeinos，V.Carbon-Based?Electronics.Nat.Nanotechnol.2007，2，605-615.
3?Son，Y.W.；Cohen，M.L.；Louie，S.G.Half-Metallic?Graphene?Nanoribbons.Nature?2006，444，347-349.
4?Schedin，F.；Geim，A.K.；Morozov，S.V.；Hill，E.M.；Blake，P.；Katsnelson，M.I.；NovoselovK，S.et?al.Detection?of?Individual?Gas?Molecules?Adsorbed?on?Graphene.Nat.Mater.2007，6，652-655.
5?Sakhaee-Pour，A.；Ahmadian，M.T.；Vafai，A.Potential?Application?of?Single-Layered?Graphene?Sheetsas?Strain?Sensor.Solid?State?Commun.2008，147，336-340.
6?Stankovich，S.；Dikin，D.A.；Dommett，G.H.B.；Kohlhaas，K.M.；Zimney，E.J.；Stach，E.A.；Pinen，R.D.；Nguyen，S.T.；Ruoff，R.S.Graphene-Based?Composite?Materials.Nature?2006，442，282-286.
7?Watcharotone，S.；Dikin，D.A.；Stankovich，S.；Piner，R.；Jung，I.；Mommett，G.H.B.；Evmenenko，G.；Wu，S.E.；Chen，S.F.；Liu，C.P.et?al.Graphene-Silica?Composite?Thin?Films?as?Transparent?Conductors.NanoLett.2007，7，1888-1892.
8?Takamura，T.；Endo，K.；Fu，L.；Wu，Y.P.；Lee，K.J.；Matsumoto，T.Identification?of?Nano-Sized?Holes?byTEM?in?the?Graphene?Layer?of?Graphite?and?the?High?Rate?Discharge?Capability?of?Li-lon?Battery?Anodes.Eletrochim.Acta?2007，53，1055-1061.
9?Novoselov，K.S.；Jiang，D.；Schedin，F.；Booth，T.J.；Khotkevich，V.V.；Morozov，S.V.；Geim，A.K.Two-Dimensional?Atomic?Crystals.Proc.Natl.Acad.Sci.USA?2005，102，10451-10453.
Graphene is by the method for machinery graphite to be rived to find at first, but the production efficiency of this method is lower, is not suitable for the production of high volume applications.People utilize the vacuum graphitizing method to go out the Graphene that ultrathin crystal is orientated in the surface growth of silicon carbide, and this method can obtain having the Graphene of patterning, is used to satisfy the needs of electron device aspect.In addition, by to expanded graphite, promptly a kind of graphite is intercalation compound under hot conditions, and rapid evaporation also can obtain Graphene, but since graphite not exclusively peel off the Graphene that can not be peeled off fully.(referring to: 1 Novoselov, K.S.; Jiang, D.; Schedin, F.; Booth, T.J.; Khotkevich, V.V.; Morozov, S.V.; Geim, A.K.Two-Dimensional Atomic Crystals.Proc.Natl.Acad.Sci.USA 2005,102,10451-10453.2 Geim, A.K.; Novoselov, K.S.The Rise ofGraphene.Nat.Mater.2007,6,183-191.)
Recently, having proposed a kind of is the softening method of raw material with graphite, promptly peel off the Graphene that obtains oxidation state to what graphite oxide carried out by microwave or ultrasonic wave, also claim to peel off the graphite oxide of attitude, and then be that reductive agent carries out chemical reduction to graphite oxide and obtains Graphene with hydrazine hydrate, sodium borohydride or Resorcinol.This method is a raw material with the graphite of cheapness, through peroxidation, peel off, reduce, realizes mass production easily, can satisfy large-scale application demand.By on the oxidation state Graphene of prereduction, introducing the Phenylsulfonic acid base, further the oxygen functional group that contains remaining on the oxidation state Graphene is thoroughly reduced again by hydrazine hydrate, obtain the sulfonated Graphene.In addition, there is report to utilize the auxiliary single stage method of ionic liquid to synthesize the Graphene of ion liquid functionalization by graphite electrochemistry.Adopt the microwave plasma CVD method in the mixed atmosphere of methane/hydrogen, on stainless steel base, to obtain abundant individual layer, bilayer and three layer graphene sheets at 500 ℃.More than all be from bottom to top method about the preparation of Graphene.Also have a kind of top-down method, obtain Graphene by the macromolecule polycyclic aromatic hydrocarbons is carried out thermal chemical reaction in the presence of rare gas element exactly.But the key of this method is will be at first by the synthetic macromolecule polycyclic aromatic hydrocarbons with two dimensional structure of the method for chemistry, and it has increased the difficulty and the cost of preparation undoubtedly.(referring to: 1.Stankovich, S.; Piner, R.D.; Chen, X.Q.; Wu, N.Q.; Nguyen, S.T.; Ruoff, R.S.Stable Aqueous Dispersionsof Graphitic Nanoplatelets via the Reduction of Exfoliated Graphite Oxide in the Presence of Poly (Sodium4-Styrenesulfonate) .J.Mater.Chem.2006,16,155-158.2.Stankovich, S.; Dikin, D.A.; Piner, R.D.; Kohlhaas, K.A.; Kleinhammes, A.; Jia, Y.Y.; Wu, Y; Nguyen, S.T.; Ruoff, R.S.Synthesis ofGraphene-Based Nanosheets via Chemical Reduction of Exfoliated Graphite Oxide.Carbon 2007,45,1558-1565.3.Li, D.; Muller, M.B.; Gilje, S.; Kaner, R B.; Wallace, G.G.Processable AqueousDispersions of Graphene Nanosheets.Nat.Nanotechnol.2008,3,101-105.4.Wang, G.X.; Yang, J.; Park, J.; Gou, X.L.; Wang, B.; Liu, H.; Yao, J.et al.Facile Synthesis and Characterization of GrapheneNanosheets.J.Phys.Chem.C.2008,112,8192-8195.5.Williams, G.; Seger, B.; Kamat, P.V.TiO
2-Graphene Nanocomposites UV-Assisted Photocatalytic Reduction of Graphene Oxide.ACS Nano 2008.2,1487-1491.6.Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F.M.; Sun, Z.Y.; De, S.; McGovern, I.T.; Holland, B.; Byrne, M.et al.High-Yield Production of Graphene by Liquid-Phase Exfoliation of Graphite.Nat.Nanotechnol.2008,3,563-568.)
At present, there is certain technological deficiency in the preparation method of graphene of having reported, as using high toxicity chemical reagent hydrazine hydrate, sodium borohydride or Resorcinol; Or need Special Equipment, as the microwave plasma CVD method, its preparation difficulty is big, cost is high, is not suitable for large-scale application demand.
Summary of the invention
In order to solve in the above-mentioned graphene preparation method environmental pollution, the preparation technological deficiency that difficulty is big, cost is high of using high toxicity chemical reagent and specialized equipment equipment to cause, the present invention is based on electrochemical principle and proposed a kind of low cost, quick, green Graphene novel preparation method.This method can prepare the rare and modified electrode of high-quality graphite, can be widely used in biosensor, electrocatalysis, the research in fields such as bioanalysis.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of electrochemical preparation method of Graphene, it is to be negative electrode with chemistry and the metal of electrochemical stability and alloy or nonmetal conductor material, the conductor material of chemistry and electrochemical stability is an anode, stir and-5～90 ℃ under, a constant voltage-1.5V～-10.0V under, electrolytic reduction oxidation state Graphene solution 1min～10h, promptly obtain the high quality Graphene or oxidation state Graphene drips of solution is coated in the also reducible Graphene that obtains in cathode material surface, be used for modified electrode as application such as bio-sensings in cathode electrode surface.
Above-mentioned preparation method, described negative electrode adopts metal and alloy or the non-metal conductor with chemistry and electrochemical stability, comprises platinum, gold and silver, copper and alloy thereof, titanium and alloy thereof, lead and alloy, graphite etc.
Above-mentioned preparation method, described anode adopts the conductor of chemistry and electrochemical stability, as graphite, platinum, plumbic oxide etc.
Above-mentioned preparation method, described oxidation state Graphene solution is graphite ultra-sonic dispersion formed yellow or transparent solution of tawny in the water again after the oxidation of Hummers ' method, concentration 0.01wt%～5wt%.
Above-mentioned preparation method, can add supporting electrolyte in the described oxidation state Graphene solution, supporting electrolyte should have chemistry and electrochemical stability, can be acid, alkali, salt is as sulfuric acid, boric acid, sodium hydroxide, potassium hydroxide, vitriol, phosphoric acid salt, muriate are as sal epsom, sodium sulfate, vitriolate of tartar, sodium-chlor, Repone K, magnesium chloride, potassiumphosphate etc.
Above-mentioned preparation method, the pH value of described oxidation state Graphene solution is 0～12.
Above-mentioned preparation method, preferably 20～50 ℃ of described electrolysis temperatures.
The present invention utilizes the graphite oxide electrochemical reduction to obtain Graphene and modified electrode thereof, and its reduction process is as follows: change the fermi level of electrode materials by the regulation and control external electric field, thereby realize effective reduction of the various oxygen-containing functional groups in graphite oxide surface.
As shown from the above technical solution, Graphene of the present invention is to utilize the contain oxygen functional group of oxidation state graphite on rare to obtain electronics be reduced on negative electrode.From technical scheme as can be known, except that electrochemical workstation of need, do not need other any specific equipment in this technical scheme, so the preparation method is simple, reaction process is easy to control, and cost is low, pollution-free, prepared graphene quality height, its technology of preparing is very easily promoted the use of.
Description of drawings
Fig. 1 is the dispersion liquid of experimental installation synoptic diagram and Graphite Electrodes and graphene oxide (a) (c) and back (b) optical photograph (d) before the reduction under-1.5V.
Fig. 2 is the cyclic voltammogram of graphene oxide modified glassy carbon electrode in the saturated 0.1mol/LPBS of nitrogen (pH=5.0) lining, sweeps speed and is 50mV/s.
Fig. 3 is-differential pulse voltammogram and the cyclic voltammogram of Graphene modified electrode in 5mmol/L hydrochloric acid of 1.3V different time electrochemical reduction, and sweep speed and be 100mV/s.
Fig. 4 is graphene oxide (a), electrochemical reduction Graphene (b) and chemical reduction Graphene (c) afm scan figure and the altitude profile figure (rapping pattern) on sheet mica.
Fig. 5 is the transmission electron microscope picture and the high-resolution-ration transmission electric-lens figure (illustration is selected area electron diffraction figure) of-1.5V electrochemical reduction Graphene, and scale is respectively 100nm, 5nm.
Fig. 6 is the infrared spectrogram of graphite (a), graphene oxide (b), electrochemical reduction Graphene (c) and chemical reduction Graphene (d).
Fig. 7 is a graphene oxide ,-1.3V electrochemical reduction 0.5min, 2min, 5min and-infrared spectrogram of 1.5V electrochemical reduction 12min.
Fig. 8 is the Raman spectrogram of electrochemical reduction Graphene (a), chemical reduction Graphene (b), graphene oxide (c) and graphite (d).
Fig. 9 is the X-ray diffractogram of graphite (a), oxidation state Graphene (b), electrochemical reduction Graphene (c) and chemical reduction Graphene (d).
Figure 10 is naked glass-carbon electrode, graphene oxide modified glassy carbon electrode, the impedance chart of chemical reduction Graphene modified glassy carbon electrode and electrochemical reduction Graphene modified glassy carbon electrode and to the catalytic cycle voltammogram (sweeping fast 200mV/s) of Dopamine HCL.
Embodiment
Quick green electrochemical production Graphene provided by the invention:
1) with graphite, glass carbon, platinum, gold and silver, copper and alloy, titanium and alloy thereof or lead and alloy electrode thereof with sand papering to minute surface, with the ultrasonic flush away surface contaminants of acetone, use 1: 1 ethanol then earlier, use the distilled water ultrasonic cleaning at last.Each 2～3min, triplicate, last N
2Air-blowing is done.
2) the analytical pure Graphite Powder 99 after the preoxidation of Hummers ' method, the oxidation (referring to 1.Kovtyukhova, N.I.; Ollivier, P.J.; Martin, B.R.; Mallouk, T.E.; Chizhik, S.A.; Buzaneva, E.V.; Gorchinskiy, A.D.Layer-by-Layer Assembly ofUltrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations.Chem.Mater.1999,11,771-778.2.Hummers, W.S.; Offeman, R.E.Preparation of Graphitic Oxide.J.Am.Chem.Soc.1958,80,1339-1339.), filtration and washing, drying are graphene oxide; With graphene oxide is that dispersion agent is made into dispersion liquid with water, and ultra-sonic dispersion is peeled off graphene oxide and obtained oxidation state Graphene solution.Gained solution is tawny, centrifugally removes unstripped graphene oxide.The concentration of graphene oxide is 2wt%, pH=6～7.
3) electrode being placed above-mentioned oxidation state Graphene solution and apply stirring, is negative electrode with the big area gauze platinum electrode; Platinum electrode is an anode; 20 ℃ of following CONTROLLED POTENTIAL are-10V that electrolytic reduction 10 hours promptly obtains black precipitate at electrode surface---Graphene 32mg.
Quick green electrochemical production Graphene provided by the invention:
The preparation method is with embodiment 1, it is negative electrode that the electrode of step 3 changes into the gold, with the plumbic oxide is anode, the concentration of graphene oxide is 1wt%, add supporting electrolyte sodium hydroxide, make pH=12, be-5.0V 50 ℃ of following CONTROLLED POTENTIAL, electrolytic reduction 2 hours promptly obtains black precipitate at electrode surface---Graphene 10mg.
Quick green electrochemical production Graphene provided by the invention:
The preparation method is with embodiment 1, it is negative electrode that the electrode of step 3 changes into graphite, with graphite is anode, the concentration of graphene oxide is 0.5wt%, add supporting electrolyte sulfuric acid, make pH=0, be-1.5V-5 ℃ of following CONTROLLED POTENTIAL, electrolytic reduction 3 hours promptly obtains black precipitate at electrode surface---Graphene 8mg.
Quick green electrochemical production Graphene provided by the invention:
The preparation method is with embodiment 1, it is negative electrode that electrode changes into the copper sheet, with platinum is anode, the concentration of graphene oxide is 0.5wt%, add supporting electrolyte sodium-chlor, make the concentration of sodium-chlor reach 0.1mol/L, be-10V 90 ℃ of following CONTROLLED POTENTIAL, electrolytic reduction 2 hours promptly obtains black precipitate at electrode surface---Graphene 6mg.
Quick green electrochemical production Graphene provided by the invention:
The preparation method is with embodiment 4, and negative electrode substitutes with silver, copper alloy, titanium or titanium alloy, and supporting electrolyte is used boric acid, potassiumphosphate or sodium-chlor instead, and other is constant, obtains the result of similar embodiment.
Graphite, graphene oxide, the specific conductivity of electrochemical reduction Graphene and chemical reduction Graphene sees Table 1.
Table 1
| Sample | Graphite | Graphene oxide | The electrochemical reduction Graphene | The chemical reduction Graphene |
| Specific conductivity | ??9.0×10 4S/m | ??2.0S/m | ??3.5×10 3S/m | ??3.2×10 3S/m |
The preparation of electrochemical reduction Graphene modified glassy carbon
With glass-carbon electrode with sand papering to minute surface, earlier, use 1: 1 ethanol then with the ultrasonic flush away surface contaminants of acetone, use the distilled water ultrasonic cleaning at last.Each 2～3min, triplicate, last N
2Air-blowing is done.With concentration is that the graphene oxide dispersant liquid drop of 0.01wt% is coated in the glass-carbon electrode surface, behind the moisture eliminator inner drying, in the acid phosphatase damping fluid, 20 ℃ of CONTROLLED POTENTIAL-1.3V electrolytic reduction 1,3,5,7,9 or 11 minutes, the functional group that the electrochemical reduction Graphene modified glassy carbon that makes is used for certain electrochemical activity of sign in 5mmol/L hydrochloric acid changed with the recovery time, differential pulse voltammogram and cyclic voltammogram are seen Fig. 3, sweep speed and are 100mV/s.But the Graphene modified glassy carbon electrode that is used for electrocatalysis is-1.5V that reduction obtains under the 12min condition.
Claims (7)
1. the electrochemical preparation method of a Graphene, it is characterized in that: it is to be negative electrode with chemistry and the metal of electrochemical stability and alloy or nonmetal conductor material, the conductor material of chemistry and electrochemical stability is an anode, stir and-5～90 ℃ under, a constant voltage-1.5V～-10.0V under, electrolytic reduction oxidation state Graphene solution 1min～10h promptly obtains the high quality Graphene in cathode electrode surface; Perhaps oxidation state Graphene drips of solution is coated in the also reducible Graphene that obtains in cathode material surface, is used for modified electrode.
2. preparation method according to claim 1 is characterized in that: described negative electrode adopts metal and alloy or the non-metal conductor with chemistry and electrochemical stability, comprises platinum, gold and silver, copper and alloy thereof, titanium and alloy thereof, lead and alloy thereof, graphite.
3. preparation method according to claim 1 is characterized in that: described anode adopts the conductor of chemistry and electrochemical stability, as graphite, platinum, plumbic oxide.
4. preparation method according to claim 1 is characterized in that: described oxidation state Graphene solution is graphite ultra-sonic dispersion formed yellow or transparent solution of tawny in the water again after the oxidation of Hummers ' method, concentration 0.01wt%～5wt%.
5. preparation method according to claim 1 is characterized in that: add supporting electrolyte in the described oxidation state Graphene solution, supporting electrolyte has chemistry and electrochemical stability, and they are acid, alkali or salt.
6. preparation method according to claim 5 is characterized in that: the pH value of described oxidation state Graphene solution is 0～12.
7. preparation method according to claim 1 is characterized in that: described electrolysis temperature is 20～50 ℃.
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