CN104649258A - Graphene-symmetrical ruthenium complex composite film and graphene self-assembly method by use of spin-coating method - Google Patents
Graphene-symmetrical ruthenium complex composite film and graphene self-assembly method by use of spin-coating method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000001338 self-assembly Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000004528 spin coating Methods 0.000 title claims abstract description 31
- 239000012327 Ruthenium complex Substances 0.000 title abstract 10
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 230000000694 effects Effects 0.000 claims abstract description 17
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 122
- 229910052707 ruthenium Inorganic materials 0.000 claims description 122
- 239000000243 solution Substances 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000002390 adhesive tape Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000005232 molecular self-assembly Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 74
- 239000010410 layer Substances 0.000 description 35
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- 238000010587 phase diagram Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 125000001165 hydrophobic group Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
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- 239000002094 self assembled monolayer Substances 0.000 description 5
- 239000013545 self-assembled monolayer Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 2
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Abstract
The invention relates to a graphene-symmetrical ruthenium complex composite film and a graphene self-assembly method by use of a spin-coating method, and belongs to the technical field of molecular self-assembly chemistry. Due to a non-covalent bond effect between a pair of pyrenyl groups in the symmetrical ruthenium complex in the graphene-symmetrical ruthenium complex composite film and the surface of HOPG, the ruthenium complex is immobilized on the surface of the HOPG; the other pair of pyrenyl groups in the symmetrical ruthenium complex is capable of immobilizing the graphene on a ruthenium complex monomolecular film by virtue of spin coating. Firstly, the self-assembly of the ruthenium complex is performed on an HOPG substrate to prepare the monomolecular film; secondly, a graphene dispersion liquid is prepared; finally, the graphene is immobilized on the ruthenium complex monomolecular film by virtue of spin coating to prepare the graphene-symmetrical ruthenium complex composite film. The prepared film has a lot of advantages, such as excellent mechanical and chemical stability, and controllable film thickness.
Description
Technical field
The present invention relates to a kind of Graphene-symmetry ruthenium complexe composite membrane and the method utilizing spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, belong to molecular self-assembling technical field of chemistry.
Background technology
Self-assembled film technology can design the structure of film on a molecular scale, obtains special performance and function, obtains huge application in electroanalysis field, becomes research field very active in recent years.Numerator self-assembly technique refers to molecule under reactive force promotes, and spontaneously forms the process with the molecular aggregate of special construction and shape.This technology is that people provide a kind of novel method effectively building various different structural-system from molecular level, huge development is achieved nearly in the past, in many research fields as all having wide practical use in nonlinear optics, molecular device, molecular biology, biosensor, surfacing engineering, anticorrosive metal in 20 years.
HOPG(Highly Oriented Pyrolytic Graphite, highly oriented pyrolytic graphite) a kind of novel high purity carbon, a kind of reusable smooth-flat-surface can be provided.HOPG has laminate structure, and usual method is first bonded on the surface of HOPG with an adhesive tape, then torn, adhesive tape will be stained with the HOPG of thin layer, and newly splitting top layer can be used as sample base material.Because HOPG has π-electronic environment, other title complexs with π-electronic environment can be connected by π-π interaction and prepare the molecular film possessing excellent properties.
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.The structure of Graphene is highly stable, and has outstanding electroconductibility and thermal conductivity.The electronics of flowing is faster in Graphene, exceedes the speed that it passes solution, so electronics meeting selecting paths naturally, through circuit.This point makes the electronics discharged be more prone to through graphenic surface just, instead of enters electrolytic solution, and Graphene is in fact a kind of transparent, good conductor, is also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.This novel nano-carbon material of Graphene has unique two-dirnentional structure and excellent electricity and optical property, adopts the electro-conductive material that graphene film comes in alternative existing electron device, and expection can the performance of the existing device of significant increase.
Domestic to utilizing the research of spin-coating method method of self-assembly Graphene in symmetry ruthenium complexe unimolecular film have not been reported at present.The self-assembling method of disclosed Graphene mainly contains:
Publication number is the Chinese patent disclosed " graphene preparation method on diamond (111) face " of CN 102102220 A, in at the diamond transition layer of Grown undoped, substrate to be placed in the cavity of hot filament Chemical Vapour Deposition system on substrate bracket, growing diamond transition layer, on diamond transition layer, grow the diamond film of B doping afterwards, self-organization of finally annealing forms Graphene.The method need be carried out under high temperature, low pressure environment.
Publication number is in the Chinese patent disclosed " preparation method of rare earth modified reduction-oxidation graphene film on surface of titanium alloy " of CN 102534586 A, first the titanium alloy sheet after cleaning is carried out hydroxylation process in aqueous sodium hydroxide solution; Secondly, self-assembly method is adopted to prepare Silan-based Thin Films on its surface, then titanium alloy substrate is put into rare earth modified graphene oxide dispersion, at the rare earth modified graphene composite thin film of its surface preparation, last heat reduction graphene oxide film, is prepared into rare earth modified reduction-oxidation graphene laminated film.The method operates under vacuo, and built-up time is long.
Publication number is in the Chinese patent of CN 102530929 A disclosed " forming the method for graphene oxide patterns and graphene pattern ", hydrophobic self-assembled monolayer is prepared on the surface at least one of substrate, UV-lamp is adopted to expose after covering described hydrophobic self-assembled monolayer with mask, and remove mask after exposure, obtain the substrate of this at least one the self-assembled monolayer template of surface containing patterning, the self-assembled monolayer template of described patterning is covered with the aqueous solution of graphene oxide quantum dot, dry, thus form graphene oxide patterns on the surface at least one of substrate.The method covers after unimolecular film at mask and needs to adopt UV-lamp exposure, in the preparation process of the aqueous solution of graphene oxide quantum dot, then need lucifuge, control pH and need carrying out in confined conditions, and built-up time is longer.
At present, unimolecular film self-assembly method is a kind of effective ways being conducive to control group assembling structure and form, can pass through covalent linkage or non covalent bond and the orderly unimolecular layer of spontaneous height of formation on the surface of electrode.Self-assembled film molecular arrangement is tight in order, but assembling process is complicated, high to equipment requirements, need carry out at clean, stopping property in good laboratory.And for making reactant and substrate active part react quickly and efficiently, title complex need have good solubleness in a solvent.In addition, ordinary method is generally be scattered in water by Graphene and title complex, long-time ultrasonic mixing, but in this method, Graphene is easily reunited, and the adhesion amount of complex molecule is few.Thus design invention a kind of orientable, self assembling process is simple, stability is high and the method be assembled into by Graphene in unimolecular film of favorable repeatability is very necessary.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of Graphene-symmetry ruthenium complexe composite membrane and the method utilizing spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film.A pair pyrenyl in the present invention in symmetry ruthenium complexe molecule and the surperficial effect by non covalent bond of HOPG, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, thus realize self-assembly Graphene in unimolecular film, method of the present invention is simple to operate, Graphene is modified evenly fully in substrate, at room temperature uses simple receptacle can operate, without the need to special conditions and equipment.In invention, specific surface area is large, electroconductibility is high, and the stable Graphene of thermochemical property is assembled in unimolecular film, effectively can improve the electrochemical activity of unimolecular film, and the plurality of advantages such as the film of preparation has good machinery and chemical stability, and the thickness of film is controlled.The present invention is achieved through the following technical solutions.
A kind of Graphene-symmetry ruthenium complexe composite membrane film, a pair pyrenyl and the surperficial effect by non covalent bond of HOPG in symmetry ruthenium complexe in this Graphene-symmetry ruthenium complexe composite membrane, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, wherein this symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2chemical general formula as follows:
。
This Graphene described-symmetry ruthenium complexe unimolecular film has characteristic light, electrochemical properties.
Utilize a method for spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, its concrete steps are as follows:
On step 1, HOPG substrate, self-assembly ruthenium complexe prepares unimolecular film: in clean container, add methylene dichloride, by symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2be dissolved in dichloromethane solution, obtained ruthenium complexe solution; By adhesive tape by being pressed in HOPG on the surface, then peeling off, obtaining new smooth conductive surface; Be immersed in by conductive surface smooth for HOPG in ruthenium complexe solution, slight concussion removing bubble, at room temperature takes out HOPG substrate after dipping, cleans up rear rare gas element dry up with methylene dichloride, and namely obtaining take HOPG as the ruthenium complexe unimolecular film of substrate;
The preparation of step 2, graphene dispersing solution: SDS is dissolved in the water and obtains the SDS aqueous solution, by graphene dispersion in the SDS aqueous solution, through ultrasonic wave dispersion treatment, centrifugation removing bottom residues, obtains graphene dispersing solution;
Step 3, the Graphene self-assembly in unimolecular film: be that the ruthenium complexe unimolecular film of substrate is fixed on and revolves on Tu instrument with HOPG by what prepare in step 1, the graphene dispersing solution that step 2 prepares is dripped on surface, start spin coating instrument, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, namely prepares Graphene-symmetry ruthenium complexe composite membrane with drying up with rare gas element after washed with methanol substrate surface removing tensio-active agent.
In described step 1, ruthenium complexe strength of solution is 50 μMs, and dipping time is 6 ~ 12h, μM representative μm ol/L.
In described step 2, the concentration of the SDS aqueous solution is 2%(w/c), the ultrasonic wave dispersion treatment time is 0.5 ~ 1.5h, and the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
In described step 3, the speed of rotation in the low rate start stage of spin coating instrument is 200rpm, and the time is 3s, and high speed rotation rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
The invention has the beneficial effects as follows:
1, hydroxyl a pair pyrenyl in this symmetry ruthenium complexe molecule and the surperficial effect by non covalent bond of HOPG, ruthenium complexe molecule is fixed on HOPG surface, another to pyrenyl by spin coating effect, Graphene is fixed in ruthenium complexe unimolecular film, thus realize fixing Graphene on self-assembled monolayer, and can prevent Graphene self from reuniting, make ruthenium complexe molecule can be attached to graphenic surface uniformly, there is the laminate structure of rule, the even single degree of scatter of Graphene in abundant guarantee material, and the ruthenium complexe molecule attached amount of graphenic surface can be increased.
2, the symmetry ruthenium complexe [Ru (Py used in the present invention
2g
1meBip)
2] (PF
6)
2in multi-solvents, there is good solubleness, be conducive to title complex and substrate active part reacts quickly and efficiently, thus improve the efficiency of self-assembly and the quality of self-assembled film.
3, the present invention adopts spin-coating method to be assembled in unimolecular film by Graphene, only needs 70 ~ 120s, greatly shortens built-up time, improve packaging efficiency, and the film of preparation has characteristic optical character.
4, preparation method of the present invention obtains Graphene assembled layers firm in unimolecular film, to the Graphene with optical, electrical character be assembled in ruthenium complexe unimolecular film, form the self assembly molecule film with optical, electrical function, Iy self-assembled layer is evenly distributed in substrate, and has good electrochemical activity and photophysical property.Electrode after modified is anode, has excellent optical, electrical chemical property, can be used for the fields such as solar cell.
5, the present invention at room temperature uses simple receptacle to operate, without the need to plant and instrument and the special conditions of complexity, the whole membrane process technique that is self-assembled into is easy to control, simple to operate, preparation cost is low, and raw material is easy to get, film forming matter is not subject to the restriction of substrate sizes and shape, the film of preparation has good machinery and chemical stability, the thickness of film and structure-controllable, and film forming is reproducible.
Accompanying drawing explanation
Fig. 1 is the AFM height map that the embodiment of the present invention 1 prepares Graphene-symmetry ruthenium complexe composite membrane;
Fig. 2 is the AFM phase diagram that the embodiment of the present invention 1 prepares Graphene-symmetry ruthenium complexe composite membrane;
Fig. 3 is the AFM height map that the embodiment of the present invention 2 prepares Graphene-symmetry ruthenium complexe composite membrane;
Fig. 4 is the AFM phase diagram that the embodiment of the present invention 2 prepares Graphene-symmetry ruthenium complexe composite membrane;
Fig. 5 is the AFM height map that the embodiment of the present invention 3 prepares Graphene-symmetry ruthenium complexe composite membrane;
Fig. 6 is the AFM phase diagram that the embodiment of the present invention 3 prepares Graphene-symmetry ruthenium complexe composite membrane.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This Graphene-symmetry ruthenium complexe composite membrane, a pair pyrenyl and the surperficial effect by non covalent bond of HOPG in symmetry ruthenium complexe in this Graphene-symmetry ruthenium complexe composite membrane, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, wherein this symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2chemical general formula as follows:
。
This utilizes the method for spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, and its concrete steps are as follows:
On step 1, HOPG substrate, self-assembly ruthenium complexe prepares unimolecular film: in clean container, add 20ml methylene dichloride, by 2.312mg symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2be dissolved in dichloromethane solution, obtained ruthenium complexe solution (concentration is 50 μMs); By adhesive tape by being pressed in HOPG on the surface, then peeling off, obtaining new smooth conductive surface; Be immersed in by conductive surface smooth for HOPG in ruthenium complexe solution, slight concussion removing bubble, takes out HOPG substrate after at room temperature flooding 6h, cleans up rear rare gas element dry up with methylene dichloride, and namely obtaining take HOPG as the ruthenium complexe unimolecular film of substrate;
The preparation of step 2, graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) be dissolved in 10ml water obtain the SDS aqueous solution (concentration is 2%(w/c)), by 2mg Graphene (Graphene,-325mesh) be dispersed in the 10mlSDS aqueous solution, through ultrasonic wave dispersion treatment 0.5h, remove bottom residues at 15krpm centrifugation 1h, obtain graphene dispersing solution;
Step 3, the self-assembly of Graphene in unimolecular film: be that the ruthenium complexe unimolecular film of substrate is fixed on and revolves on Tu instrument with HOPG by what prepare in step 1, the graphene dispersing solution that step 2 prepares is dripped on surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 700r/min, time is 120s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, namely Graphene-symmetry ruthenium complexe composite membrane is prepared with drying up with rare gas element after washed with methanol substrate surface removing tensio-active agent.
The surface contact angle test of the Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane: the contact angle on the HOPG surface after surface treatment is 61.6 °, the surface contact angle of the HOPG after NW-TFT ruthenium complexe unimolecular film is 81.5 °, improve surface hydrophobicity, this is because electrode surface is the hydrophobic group in exposed ruthenium complexe molecule, in ruthenium complexe unimolecular film after self-assembly Graphene, the contact angle of substrate surface is 59.9 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduce the hydrophobicity of substrate surface.Meanwhile, the change of contact angle to also demonstrate in symmetry ruthenium complexe unimolecular film successfully assembling and has gone up Graphene.
The Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane AFM tests: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can clearer research Graphene surface topography size and height, carried out further research by atomic force microscope to it, Fig. 1 is the AFM figure of the substrate in ruthenium complexe unimolecular film after self-assembly Graphene obtained prepared by the implementation case.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1 ~ 15nm from data plot, the Graphene number of plies of that is assembling is 1 ~ 15 layer.
For determining the assembling area of graphene layer, still characterize with the graphene layer of atomic force microscope to preparation, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 2.Can find out roughly from Fig. 2 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 2 calculates, the fraction of coverage obtaining graphene layer is 95.6%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
Embodiment 2
This Graphene-symmetry ruthenium complexe composite membrane, a pair pyrenyl and the surperficial effect by non covalent bond of HOPG in symmetry ruthenium complexe in this Graphene-symmetry ruthenium complexe composite membrane, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, wherein this symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2chemical general formula as follows:
。
This utilizes the method for spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, and its concrete steps are as follows:
On step 1, HOPG substrate, self-assembly ruthenium complexe prepares unimolecular film: in clean container, add 20ml methylene dichloride, by 2.312mg symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2be dissolved in dichloromethane solution, obtained ruthenium complexe solution (concentration is 50 μMs); By adhesive tape by being pressed in HOPG on the surface, then peeling off, obtaining new smooth conductive surface; Be immersed in by conductive surface smooth for HOPG in ruthenium complexe solution, slight concussion removing bubble, takes out HOPG substrate after at room temperature flooding 9h, cleans up rear rare gas element dry up with methylene dichloride, and namely obtaining take HOPG as the ruthenium complexe unimolecular film of substrate;
The preparation of step 2, graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) be dissolved in 10ml water obtain the SDS aqueous solution (concentration is 2%(w/c)), by 2mg Graphene (Graphene,-325mesh) be dispersed in the 10mlSDS aqueous solution, through ultrasonic wave dispersion treatment 1h, remove bottom residues at 15krpm centrifugation 2h, obtain graphene dispersing solution;
Step 3, the self-assembly of Graphene in unimolecular film: be that the ruthenium complexe unimolecular film of substrate is fixed on and revolves on Tu instrument with HOPG by what prepare in step 1, the graphene dispersing solution that step 2 prepares is dripped on surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 800r/min, time is 100s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, namely Graphene-symmetry ruthenium complexe composite membrane is prepared with drying up with rare gas element after washed with methanol substrate surface removing tensio-active agent.
The surface contact angle test of the Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane: the contact angle on the HOPG surface after surface treatment is 59.6 °, the surface contact angle of the HOPG after NW-TFT ruthenium complexe unimolecular film is 81.3 °, improve surface hydrophobicity, this is because electrode surface is the hydrophobic group in exposed ruthenium complexe molecule, in ruthenium complexe unimolecular film after self-assembly Graphene, the contact angle of substrate surface is 62.0 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduce the hydrophobicity of substrate surface.Meanwhile, the change of contact angle to also demonstrate in symmetry ruthenium complexe unimolecular film successfully assembling and has gone up Graphene.
The Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane AFM tests: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can clearer research Graphene surface topography size and height, carried out further research by atomic force microscope to it, Fig. 3 is the AFM figure of the substrate in ruthenium complexe unimolecular film after self-assembly Graphene obtained prepared by the implementation case.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1 ~ 16nm from data plot, the Graphene number of plies of that is assembling is 1 ~ 16 layer.
For determining the assembling area of graphene layer, still characterize with the graphene layer of atomic force microscope to preparation, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 4.Can find out roughly from Fig. 4 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 4 calculates, the fraction of coverage obtaining graphene layer is 95.1%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
Embodiment 3
This Graphene-symmetry ruthenium complexe composite membrane, a pair pyrenyl and the surperficial effect by non covalent bond of HOPG in symmetry ruthenium complexe in this Graphene-symmetry ruthenium complexe composite membrane, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, wherein this symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2chemical general formula as follows:
。
This utilizes the method for spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, and its concrete steps are as follows:
On step 1, HOPG substrate, self-assembly ruthenium complexe prepares unimolecular film: in clean container, add 20ml methylene dichloride, by 2.312mg symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2be dissolved in dichloromethane solution, obtained ruthenium complexe solution (concentration is 50 μMs); By adhesive tape by being pressed in HOPG on the surface, then peeling off, obtaining new smooth conductive surface; Be immersed in by conductive surface smooth for HOPG in ruthenium complexe solution, slight concussion removing bubble, takes out HOPG substrate after at room temperature flooding 12h, cleans up rear rare gas element dry up with methylene dichloride, and namely obtaining take HOPG as the ruthenium complexe unimolecular film of substrate;
The preparation of step 2, graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) be dissolved in 10ml water obtain the SDS aqueous solution (concentration is 2%(w/c)), by 2mg Graphene (Graphene,-325mesh) be dispersed in the 10mlSDS aqueous solution, through ultrasonic wave dispersion treatment 1.5h, remove bottom residues at 15krpm centrifugation 3h, obtain graphene dispersing solution;
Step 3, the self-assembly of Graphene in unimolecular film: be that the ruthenium complexe unimolecular film of substrate is fixed on and revolves on Tu instrument with HOPG by what prepare in step 1, the graphene dispersing solution that step 2 prepares is dripped on surface, start spin coating instrument, low rate start stage speed of rotation is 200r/min, time is 3s, high speed rotation rate is 1000r/min, time is 70s, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, namely Graphene-symmetry ruthenium complexe composite membrane is prepared with drying up with rare gas element after washed with methanol substrate surface removing tensio-active agent.
The surface contact angle test of the Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane: the contact angle on the HOPG surface after surface treatment is 60.1 °, the surface contact angle of the HOPG after NW-TFT ruthenium complexe unimolecular film is 81.3 °, improve surface hydrophobicity, this is because electrode surface is the hydrophobic group in exposed ruthenium complexe molecule, in ruthenium complexe unimolecular film after self-assembly Graphene, the contact angle of substrate surface is 61.0 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complexe, substrate surface is Graphene, reduce the hydrophobicity of substrate surface.Meanwhile, the change of contact angle to also demonstrate in symmetry ruthenium complexe unimolecular film successfully assembling and has gone up Graphene.
The Graphene that the present embodiment prepares-symmetry ruthenium complexe composite membrane AFM tests: because single-layer graphene is difficult to be observed under scanning electronic microscope (SEM), only could observe clearly under atomic force microscope (AFM).Atomic force microscope characterizes Graphene the most direct means.In order to can clearer research Graphene surface topography size and height, carried out further research by atomic force microscope to it, Fig. 5 is the AFM figure of the substrate in ruthenium complexe unimolecular film after self-assembly Graphene obtained prepared by the implementation case.Clearly can see the laminated structure of graphene layer from afm image, can see that Graphene thickness is 1 ~ 15nm from data plot, the Graphene number of plies of that is assembling is 1 ~ 15 layer.
For determining the assembling area of graphene layer, still characterize with the graphene layer of atomic force microscope to preparation, setting scan size is 10 μm × 10 μm, obtains the AFM phase diagram of graphene layer, as shown in Figure 6.Can find out roughly from Fig. 6 that graphene layer is evenly distributed in substrate, fully, for clearly concrete Graphene area coverage, the area of application area software for calculation to the graphene layer in AFM phase diagram in Fig. 4 calculates, the fraction of coverage obtaining graphene layer is 95.4%, illustrate that graphene layer is comparatively large at suprabasil assembling area, assemble more abundant.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (5)
1. Graphene-symmetry ruthenium complexe composite membrane, it is characterized in that: a pair pyrenyl and the surperficial effect by non covalent bond of HOPG in symmetry ruthenium complexe in this Graphene-symmetry ruthenium complexe composite membrane, ruthenium complexe molecule is fixed on HOPG surface, Graphene is fixed in ruthenium complexe unimolecular film to pyrenyl by spin coating effect by another, wherein this symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2chemical general formula as follows:
。
2. utilize a method for spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film, it is characterized in that concrete steps are as follows:
On step 1, HOPG substrate, self-assembly ruthenium complexe prepares unimolecular film: in clean container, add methylene dichloride, by symmetry ruthenium complexe [Ru (Py
2g
1meBip)
2] (PF
6)
2be dissolved in dichloromethane solution, obtained ruthenium complexe solution; By adhesive tape by being pressed in HOPG on the surface, then peeling off, obtaining new smooth conductive surface; Be immersed in by conductive surface smooth for HOPG in ruthenium complexe solution, slight concussion removing bubble, at room temperature takes out HOPG substrate after dipping, cleans up rear rare gas element dry up with methylene dichloride, and namely obtaining take HOPG as the ruthenium complexe unimolecular film of substrate;
The preparation of step 2, graphene dispersing solution: SDS is dissolved in the water and obtains the SDS aqueous solution, by graphene dispersion in the SDS aqueous solution, through ultrasonic wave dispersion treatment, centrifugation removing bottom residues, obtains graphene dispersing solution;
Step 3, the Graphene self-assembly in unimolecular film: be that the ruthenium complexe unimolecular film of substrate is fixed on and revolves on Tu instrument with HOPG by what prepare in step 1, the graphene dispersing solution that step 2 prepares is dripped on surface, start spin coating instrument, make graphene dispersing solution uniform spreading film forming, room temperature is placed and is made its seasoning, namely prepares Graphene-symmetry ruthenium complexe composite membrane with drying up with rare gas element after washed with methanol substrate surface removing tensio-active agent.
3. the method utilizing spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film according to claim 2, it is characterized in that: in described step 1, ruthenium complexe strength of solution is 50 μMs, dipping time is 6 ~ 12h.
4. the method utilizing spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film according to claim 2, it is characterized in that: in described step 2, the concentration of the SDS aqueous solution is 2%, the ultrasonic wave dispersion treatment time is 0.5 ~ 1.5h, the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
5. the method utilizing spin-coating method self-assembly Graphene in symmetry ruthenium complexe unimolecular film according to claim 2, it is characterized in that: in described step 3, the speed of rotation in the low rate start stage of spin coating instrument is 200rpm, time is 3s, high speed rotation rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
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