CN104681282B - A kind of graphene-based compound functional film material and preparation method thereof - Google Patents
A kind of graphene-based compound functional film material and preparation method thereof Download PDFInfo
- Publication number
- CN104681282B CN104681282B CN201410841639.2A CN201410841639A CN104681282B CN 104681282 B CN104681282 B CN 104681282B CN 201410841639 A CN201410841639 A CN 201410841639A CN 104681282 B CN104681282 B CN 104681282B
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- ruthenium complex
- ultra
- pure water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses graphene-based compound functional film material of one kind and preparation method thereof, belong to field of composite material preparation, the present invention is alternately self-assembled to amphipathic ruthenium complex molecular film and symmetry ruthenium complex molecular film on graphene-based bottom using LBL self-assembly method, compound functional membrane is formed, wherein amphipathic ruthenium complex is [Ru (Py2G1MeBip)(XPOH)] (PF6)2, symmetry ruthenium complex is [Ru (XPOH)2](PF6)2；The composite membrane that the present invention is obtained modifies uniform abundant in conductive substrates, with good mechanically and chemically stability, combines the respective advantage of material, chemical property and stability are significantly improved.The present invention is at room temperature operable using simple receptacle, without specific condition and the instrument of complex and expensive, compared with other laminated assembling technologies, easy to operate, built-up time of the invention is short, do not influenceed by base material and shape, film and substrate bond strength it is high, with preferable application value.
Description
Technical field
The present invention relates to graphene-based compound functional film material of one kind and preparation method thereof, belong to composite and prepare neck
Domain.
Background technology
Because modern device is just being strided forward to molecular level step by step, therefore information processing is carried out on a molecular scale and is deposited
The research of storage has very tempting prospect.The conventional method of molecule assembling has LB membrane technologies, numerator self-assembly technique, molecular beam
Epitaxial growth and atomic force process technology etc..LB films, which have the problems such as stability difference and the contact with interface, to be solved.
Molecular beam epitaxial growth and atomic force processing are because its equipment is complicated, expensive and can not prepare the film of large area and make it
Using being restricted.And molecular self-assembling is in an equilibrium condition, by covalent bond or non-covalent interaction, spontaneously
Association forms the two dimension or the process of Magnetic Properties of Three-Dimensional Supramolecular Complex of stable, perfect structure.Compared with other technologies, self-assembling technique is not only
Have the advantages that LB membrane technologies can accurately control thickness, and ideally solve connecing between functional material and electrode of substrate
Boundary's problem.Functional molecular is by component of the self assembly film forming ability formation with specific function, and different components can be by certainly
Package technique, is assembled into various ultra-thin microelectronic devices.Therefore, numerator self-assembly technique has huge in molectronics
Big application prospect.
Self-assembled multilayer film is carried out on the basis of self-assembled monolayer, and it requires to carry out on the surface of self-assembled monolayer
Hydroxyl, carboxyl, ester group, P (OH) in chemical modification, connection3, amino, halogen etc., these surface active groups can be directly used for
Next layer of assembling, or function base etc. is transformed into by chemical reaction, so as to be conducive to next layer of assembling.Obtained functionalization
Surface can proceed with secondary self assembly and functionalization again, so repeat that multilayer self-assembled film can be obtained.Such multilayer knot
Structure is progressively assembled, thus its structure can be strictly controlled by, while changing functional molecular between layers, can be obtained
High-sequential, Various Functions self assembling multilayer structure.
Ruthenium outermost layer has 4d75s1Structure, the common valence state of its ion is Ru (I), Ru (II) and Ru (III), and ruthenium is easy to shape
It is abundant into the complex of hexa-coordinate and variation of valence itself, it is had abundant physicochemical property.Ruthenium complex thermodynamics is steady
Qualitative good, photochemical light physical message is abundant, the active high and long lifespan of excited state reaction and luminescent properties are good.Therefore its is current
It is widely used in chemiluminescence, electro transfer, nonlinear optical material, molecular light switch, molecular recognition, the field such as sensor
Research.Ruthenium complex toxicity is low simultaneously, and what is easily absorbed and can drain quickly makes it have huge application in anti-tumor aspect.
Ruthenium complex also has great significance in terms of chemical industry sensitization catalysis in itself.Therefore research ruthenium complex is to industrial agriculture national defence
Medicine is all significant.
Graphene（Graphene）It is a kind of new material for the individual layer laminated structure being made up of carbon atom.It is a kind of former by carbon
Son is with sp2Hybridized orbit composition hexangle type is in the flat film of honeycomb lattice, is most thin, the most hard nanometer material in known world
Material, it is almost fully transparent, is the minimum material of world resistivity.Because graphene is substantially a kind of transparent, good
Conductor, also be adapted for for manufacturing transparent touch screen, even tabula rasa, solar cell.
The domestic research to the preparation method of graphene-based compound functional film material at present has not been reported.Disclosed point
The self-assembling method of sub- film mainly has：
In the A of Publication No. CN 102912333 " method that thermal electric film is prepared using LBL self-assembly ", make first
Standby persursor material, then carries out proton exchange, obtains proton exchange product, then carries out ion friendship to proton exchange product again
Change, obtain intercalation product, then intercalation product is peeled off, obtain peeling off product, nano flake suspension is centrifuged, utilize
Substrate carries out lifting, Best-Effort request or immersion manually to the nano flake suspension after centrifugation, i.e., thermoelectricity is formed in substrate thin
Film.The preparation of presoma need to be carried out under the high temperature conditions in this method.
In the A of Publication No. CN 103922326 " a kind of preparation method of interface self assembly sulfonated graphene film ",
Scattered sulfonated graphene solution is injected into the aqueous phase of the oil-water interface established, sulfonated graphene is in oil-hydrosphere
Face carries out self assembly, removes after oil phase and vertically to be lifted again by the way that target substrate is dipped vertically into solution, by sulfonated graphene film
It is transferred to target substrate and obtains sulfonated graphene film.This method is carried out under vacuum conditions.
A kind of A of Publication No. CN 103993342 " one-dimensional orderly TiO of self assembly2Nanotube/graphene oxide is combined
In the preparation method of material ", the electrolyte containing graphene oxide is prepared, Ti pieces rear oxidation is handled after cleaning, be cleaned and dried, obtain
To unbodied TiO2Nanotube/graphene oxide composite material, is thermally treated resulting in the orderly TiO of the one-dimensional self assembly of Detitanium-ore-type2
Nanotube/graphene oxide composite material.This method is heat-treated and requires that Ti pieces are that purity is under vacuum
99.6% high-purity titanium sheet.
At present, molecular film self-assembly method is a kind of effective ways for being conducive to controlling package assembly and form, self-assembled film
Molecules align is close in order, compound with regular structure, but assembling process is complicated, high to equipment requirement, need to be preferably real in clean, seal
Test indoor progress.The stability of the film of generation multipair heat, chemical environment, time and external pressure greatly is poor, while the preparation of film
The film groove and strict substrate of costliness are needed, in addition to substrate, solution concentration, pH, cleaning and adsorption time etc. can influence assembling
Quality.Moreover, to make reactant quickly and efficiently be reacted with substrate active part, it is desirable to which complex need to have preferably in a solvent
Solubility.Thus design invention is a kind of orientable, self assembling process is simple and can form that stability is high, reproducible, film layer
Adjustable molecule film method is very necessary.
The content of the invention
The problem of existing for above-mentioned prior art and deficiency, the present invention provide a kind of graphene-based compound function membrane material
Pyrenyl in material, amphipathic ruthenium complex molecule is self-assembled on graphene-based bottom by the effect of non-covalent bond, then will be certainly
Graphene-based bottom after assembling repeats alternating impregnating in zirconyl chloride solution and symmetry ruthenium complex solution, passes through zirconium ion
It will connect, obtain between amphipathic ruthenium complex molecule and symmetry ruthenium complex molecule, and symmetry ruthenium complex molecule
The number of plies and the adjustable composite film material of thickness.The compound functional film material joint multiple material that the present invention is obtained is respective excellent
Point, chemical property and stability are significantly improved compared with single self-assembled film.The present invention is at room temperature using simple appearance
Device is operable, without specific condition and the instrument of complex and expensive.
Amphipathic ruthenium complex [Ru (Py in the present invention2G1MeBip)(XPOH)] (PF6)2Chemical formula it is as follows：
；
Symmetry ruthenium complex [Ru (XPOH) 2](PF6)2Chemical formula it is as follows：
。
With reference to patent application 201410450980.5, " a kind of dye-sensitized solar cells use two to the amphipathic ruthenium complex
Method is obtained in parent's property benzimidazole ruthenium complex and preparation method thereof ".
The symmetry ruthenium complex with reference to patent application 201410636069.3, " match somebody with somebody by a kind of symmetry benzimidazole ruthenium
Method is obtained in compound and preparation method thereof ".
The above method is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：Ultra-pure water is added in clean container, pH to 10 is modulated with ammoniacal liquor
~ 12, weigh a certain amount of amphipathic ruthenium complex [Ru (Py2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water, uses HCl
Adjust after pH to 5 ~ 6,10 ~ 100 μM of amphipathic ruthenium complex solution is made；
（2）The preparation of zirconyl chloride solution：A certain amount of zirconium oxychloride is weighed in clean container and is dissolved in ultra-pure water
In solution, 10 ~ 30mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：Ultra-pure water is added in clean container, pH to 10 is modulated with ammoniacal liquor
~ 12, weigh a certain amount of symmetry ruthenium complex [Ru (XPOH)] (PF6)2It is dissolved in ultra-pure water, pH to 5 ~ 6 is adjusted with HCl
Afterwards, 10 ~ 100 μM of symmetry ruthenium complex solution is made；
（4）The preparation of graphene dispersing solution：By lauryl sodium sulfate（SDS）It is dissolved in the water and obtains 2%（Quality volume
Than w/v）The SDS aqueous solution, by graphene dispersion in the SDS aqueous solution (quality of graphene and the volume ratio of the SDS aqueous solution
For 2:10~4:10, mg/ml), centrifuged after ultrasonic wave decentralized processing and remove bottom residues, obtain concentration for 0.1 ~ 0.3mg/
Ml graphene dispersing solution；
（5）The hydrophilic treated of ITO conductive glass surfaces：RCA solution is prepared in beaker, ITO substrates RCA is immersed in molten
In liquid, slight concussion is moved in water-bath after removing bubble, is taken out ITO substrates after 0.5 ~ 2h of heating and is cleaned with ultra-pure water, inertia
Gas is dried up；
（6）The preparation at graphene-based bottom：By step（5）Obtained ITO substrates are fixed on rotation Tu instrument, and step is added dropwise（4）
The middle graphene dispersing solution configured, starting spin coating instrument makes graphene dispersing solution uniformly sprawl film forming on ITO substrates, and room temperature is put
Putting spontaneously dries it, with methanol clean substrate remove SDS surfactants after with inert gas drying obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in, slight concussion removes bubble, and base is taken out after impregnating 6 ~ 12h at room temperature
Piece cleans up rear inert gas drying with ultra-pure water；
（8）The assembling of symmetry ruthenium complex molecular film：By step（7）Obtained substrate is immersed in step（2）In oxygen
Chlorination zirconium solution, impregnates the clean inert gas drying of substrate ultra-pure water is taken out after 1.5 ~ 3.5h at room temperature, be then immersed in step
Suddenly（3）In symmetry ruthenium complex solution in, slight concussion removes bubble, and substrate is taken out after impregnating 3 ~ 6h at room temperature, uses
Ultra-pure water cleans inert gas drying；
（9）Repeat step（8）, the number of plies and the adjustable compound functional film material of thickness are obtained, wherein the 1st layer is graphene
Film, the 2nd layer is amphipathic ruthenium complex molecular film, the 3rd and using upper strata as symmetry ruthenium complex molecular film.
The step（4）The middle ultrasonic wave decentralized processing time be 0.5 ~ 1.5h, it is ultrasonically treated after centrifuge the time be 1 ~
3h, rotating speed is 15krpm.
The step（5）In RCA solution be ammoniacal liquor, H2O21 is pressed with ultra-pure water:1:The solution of 5 ratio mixing, water-bath
Heating-up temperature is 90 DEG C.
The step（6）In, the low rate start stage speed of rotation of spin coating instrument is 200rpm, and the time is 1 ~ 3s, is revolved at a high speed
Rotational speed rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
The beneficial effects of the invention are as follows：
1st, the pyrenyl and graphenic surface in amphipathic ruthenium complex molecule by the effect of non-covalent bond by amphipathic ruthenium
Complex molecule is self-assembled on graphene-based bottom, and amphipathic ruthenium complex molecule and symmetry can be then connected by zirconium ion
Ruthenium complex molecule, repeats alternating impregnating zirconyl chloride solution and symmetry ruthenium complex solution, so as to realize the number of plies and thickness
The self assembly of adjustable composite membrane.
2nd, amphipathic ruthenium complex [Ru (Py are made full use of in the present invention2G1MeBip)(XPOH)] (PF6)2And symmetry
Ruthenium complex [Ru (XPOH)2](PF6)2There is the advantage of preferable solubility in multi-solvents, so as to promote complex and base
Piece active part is fast and efficiently reacted, so as to improve the efficiency of self assembly and the quality of self-assembled film.
3rd, the compound functional membrane that the present invention is obtained modifies uniform abundant in conductive substrates, with good machinery and change
Stability is learned, two kinds of ruthenium complexes and graphene, which are combined assembling, can combine the respective advantage of multiple material, with single from group
Dress film is significantly improved compared to chemical property and stability.Electrode through compound function after film modified has excellent electrification
Activity is learned, it is anode that can be used as, applied to fields such as solar cells.
4th, the present invention is operable using simple receptacle at room temperature, without specific condition and the instrument of complex and expensive, with
Other laminated assembling technologies are compared, and the whole membrane process technique that is self-assembled into of the present invention is easily controllable, simple to operate, built-up time
Extremely short, preparation cost is low, and raw material is easy to get, and composite membrane is high with substrate bond strength, and film forming matter is not limited by substrate sizes and shape
System, the film of preparation has good mechanically and chemically stability, the thickness and structure-controllable of film, and film forming is reproducible.
Brief description of the drawings
Fig. 1 is the surface contact angle for the compound functional membrane that the embodiment of the present invention 1 is prepared with the change of the assembling number of plies
Situation；
Fig. 2 be compound function that the embodiment of the present invention 1 is prepared it is film modified after graphene-based bottom cyclic voltammetric
Figure；
Fig. 3 is the surface contact angle for the compound functional membrane that the embodiment of the present invention 2 is prepared with the change of the assembling number of plies
Situation；
Fig. 4 be compound function that the embodiment of the present invention 2 is prepared it is film modified after graphene-based bottom cyclic voltammetric
Figure；
Fig. 5 is the surface contact angle for the compound functional membrane that the embodiment of the present invention 3 is prepared with the change of the assembling number of plies
Situation；
Fig. 6 be compound function that the embodiment of the present invention 3 is prepared it is film modified after graphene-based bottom cyclic voltammetric
Figure.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1：It is non-that this graphene-based compound functional film material is that pyrenyl in amphipathic ruthenium complex molecule passes through
The effect of covalent bond is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxygen chlorine
Change in zirconium solution and symmetry ruthenium complex solution, by zirconium ion by amphipathic ruthenium complex molecule and symmetry ruthenium complex
Connected between molecule, and symmetry ruthenium complex molecule, the number of plies and the adjustable composite film material of thickness are obtained, wherein amphipathic
The chemical formula of ruthenium complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
。
The preparation method of the graphene-based compound functional film material and preparation method thereof, it is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：10ml ultra-pure waters are added in clean beaker, pH is modulated with ammoniacal liquor
To 10,1.943mg amphipathic ruthenium complex [Ru (Py are weighed2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water, uses
HCl is adjusted after pH to 5, addition ultra-pure water to 15ml, produces 50 μM of ruthenium complex solution；
（2）The preparation of zirconyl chloride solution：20ml ultra-pure waters are added in clean beaker, 128.8mg oxychlorination is weighed
Zirconium is dissolved in ultra-pure water solution, and 20mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：10ml ultra-pure waters are added in clean beaker, pH is modulated with ammoniacal liquor
To 10,1.718mg ruthenium complexes [Ru (XPOH) is weighed2](PF6)2It is dissolved in solution, is adjusted with HCl after pH to 5, is added super
Pure water produces 50 μM of symmetry ruthenium complex solution to 15ml；
（4）The preparation of graphene dispersing solution：By 0.2g lauryl sodium sulfate（SDS）It is dissolved in 10ml water and obtains 2%
（w/v）The SDS aqueous solution, by 4mg graphenes（Graphene, -325mesh）It is dispersed in the 10ml SDS aqueous solution, ultrasonic wave
Moved to after decentralized processing 0.5h in centrifuge, 1h is centrifuged under 15krpm rotating speeds, remove bottom residues, obtaining concentration is
0.3mg/ml graphene dispersing solutions；
（5）The hydrophilic treated of ITO conductive glass surfaces：By NH3、H2O21 is pressed with ultra-pure water:1:5 volume ratio mixed preparing
RCA solution, ITO substrates are immersed in RCA solution and just faced outwardly, and slight shake away is moved in water-bath after bubble, 90
DEG C heating 0.5h after take out ITO substrates with ultra-pure water clean, nitrogen drying；
（6）The preparation at graphene-based bottom：By step（5）In surface hydrophilic processing after ITO substrates be fixed on rotation Tu
On instrument, step is added dropwise（4）The middle graphene dispersing solution configured, the spin coating instrument low rate start stage speed of rotation is 200rpm, when
Between be 1s, high speed rotation rate is 700rpm, and the time is 120s, graphene dispersing solution is uniformly sprawled film forming, and room temperature, which is placed, to be made
Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with nitrogen dry up obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in just face outwardly, slight concussion removes bubble, is taken after impregnating 6h at room temperature
Go out ITO substrates ultra-pure water and clean nitrogen drying；
（8）The assembling of symmetry ruthenium complex molecular film：By step（7）Obtained substrate is immersed in step（2）In oxygen
Chlorination zirconium solution, takes out substrate ultra-pure water after 1.5h after impregnating at room temperature and cleans nitrogen drying, be then immersed in step（3）In
Symmetry ruthenium complex solution in, slight concussion removes bubble, impregnates ITO substrates are taken out after 3h at room temperature, use ultra-pure water
Clean nitrogen drying.
（9）Repeat step（8）, the compound functional membrane that the number of plies is 4 layers is obtained, wherein the 1st layer is graphene film, the 2nd layer
For amphipathic ruthenium complex molecular film, the 3rd, 4 layers be symmetry ruthenium complex molecular film.
The surface contact angle test for the compound functional membrane that the present embodiment is prepared：The ITO bases of surface hydrophilic before processing
The contact angle on piece surface is 86.9 °, and it is hydrophobicity to illustrate cleaning ITO surfaces；ITO substrate surfaces after surface hydrophilic processing connect
Feeler is 66.1 °, it was demonstrated that the hydrophilic treatment method of the present invention improves the hydrophily on ITO surfaces；Assemble the first layer graphene
Surface contact angle after film is 60.9 °, and substrate surface at this moment is graphene film；Assemble after the amphipathic ruthenium complex film of the second layer
Surface contact angle be 52.3 °, improve surface hydrophilicity because the hydrophobic group in amphipathic ruthenium complex be fixed to stone
Black alkene surface, hydrophilic group is exposed on surface, show the substrate surface after the amphipathic ruthenium complex molecular film of assembling hydrophilic
Property；Continue to assemble after film layer, the contact angle of substrate surface slightly about changes at substantially 51 °, as shown in Figure 1.
The electrochemical property test for the substrate through compound function after film modified that the present embodiment is prepared：After modification
Substrate be anode, using cyclic voltammetry judge to after modification substrate carry out cyclic voltammetric test.Test instrument
The AL660-C electrochemical analysers produced for BAS companies of the U.S., parameter setting is as follows：Initial potential is 0 V；High potential is
1.2V；Low potential is 0 V；Scanning at initial stage is Poaitive；Scanning times are 6 times；Stand-by period is 3~5 s；Sensitivity is selected
For 10 μ A；Filtering parameter is 50 Hz；Multiplication factor 1；Sweep speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1 MTBAPF in continuous mode6Solution（Solvent is anhydrous MeCN）As electrolyte, make
With 3h is preceding dried under vacuum, the substrate after modification is used as working electrode, Ag/AgNO3As reference electrode, Pt lines are as a comparison
Electrode.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential correction.After being modified
The voltammogram of substrate is as shown in Figure 2.
The quantity of electric charge and amount of coating of ITO substrate press formula respectively（1）With（2）Calculated.
（1）
Wherein, Q：The quantity of electric charge, C；
A：Peak area, dots；
B：Chosen region B area, dots；
IB：B electric current, A；
PB：B voltage, V；
V：Sweep speed, V/s.
（2）
Wherein, Г：Amount of coating, mol/cm2；
Q：The quantity of electric charge, C；
F：Faraday constants, 96485C/mol；
n：Electron number；
A：Contact area, 0.26cm2。
According to formula（1）With（2）Calculate obtain be through the quantity of electric charge on graphene-based bottom of the 4 layers of compound function after film modified
5.624×10-6C, amount of coating is 1.121 × 10-10 mol/cm2。
Embodiment 2：Graphene-based compound functional film material, is that the pyrenyl in amphipathic ruthenium complex molecule passes through non-co-
The effect of valence link is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxychlorination
In zirconium solution and symmetry ruthenium complex solution, amphipathic ruthenium complex molecule and symmetry ruthenium complex are divided by zirconium ion
Connected between son, and symmetry ruthenium complex molecule, the number of plies and the adjustable composite film material of thickness are obtained, wherein amphipathic ruthenium
The chemical formula of complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
。
The preparation method of the graphene-based compound functional film material, it is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：10ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 10.5,2.590mg amphipathic ruthenium complex [Ru (Py are weighed2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water,
Adjusted with HCl after PH to 5.5, addition ultra-pure water to 20ml, produce 50 μM of ruthenium complex solution；
（2）The preparation of zirconyl chloride solution：25ml ultra-pure waters are added in clean beaker, 161mg zirconium oxychlorides are weighed
It is dissolved in ultra-pure water solution, 20mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：10ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 10.5,2.291mg ruthenium complexes [Ru (XPOH) is weighed2](PF6)2It is dissolved in solution, is adjusted with HCl after PH to 5.5, plus
Enter ultra-pure water to 20ml, produce 50 μM of symmetry ruthenium complex solution；
（4）The preparation of graphene dispersing solution：By 0.2g lauryl sodium sulfate（SDS）It is dissolved in 10ml water and obtains 2%
（w/v）The SDS aqueous solution, by 3.5mg graphenes（Graphene, -325mesh）It is dispersed in the 10ml SDS aqueous solution, ultrasound
Moved to after ripple decentralized processing 1h in centrifuge, 2.5h is centrifuged under 15krpm rotating speeds, remove bottom residues, obtaining concentration is
0.26mg/ml graphene dispersing solution；
（5）The hydrophilic treated of ITO conductive glass surfaces：By NH3、H2O21 is pressed with ultra-pure water:1:5 volume ratio mixed preparing
RCA solution, ITO substrates are immersed in RCA solution and just faced outwardly, and slight shake away is moved in water-bath after bubble, 90
DEG C heating 1h after take out ITO substrates with ultra-pure water clean, nitrogen drying；
（6）The preparation at graphene-based bottom：By step（5）In surface hydrophilic processing after ITO substrates be fixed on rotation Tu
On instrument, step is added dropwise（4）The middle graphene dispersing solution configured, the spin coating instrument low rate start stage speed of rotation is 200rpm, when
Between be 2s, high speed rotation rate is 800rpm, and the time is 100s, graphene dispersing solution is uniformly sprawled film forming, and room temperature, which is placed, to be made
Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with nitrogen dry up obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in just face outwardly, slight concussion removes bubble, is taken after impregnating 9h at room temperature
Go out ITO substrates ultra-pure water and clean nitrogen drying；
（8）The assembling of symmetry ruthenium complex molecular film：By step（7）Obtained substrate is immersed in step（2）In oxygen
Chlorination zirconium solution, takes out substrate ultra-pure water after 2h after impregnating at room temperature and cleans nitrogen drying, be then immersed in being immersed in step
（3）In symmetry ruthenium complex solution in, slight concussion removes bubble, impregnates ITO substrates are taken out after 4.5h at room temperature, use
Ultra-pure water cleans nitrogen drying；
（9）Repeat step（8）, the compound functional membrane that the number of plies is 5 layers is obtained, wherein the 1st layer is graphene film, the 2nd layer
For amphipathic ruthenium complex molecular film, the 3rd, 4,5 layers be symmetry ruthenium complex molecular film.
The surface contact angle test for the compound functional membrane that the present embodiment is prepared：The ITO bases of surface hydrophilic before processing
The contact angle on piece surface is 86.0 °, and it is hydrophobicity to illustrate cleaning ITO surfaces；ITO substrate surfaces after surface hydrophilic processing connect
Feeler is 67.1 °, it was demonstrated that the hydrophilic treatment method of the present invention improves the hydrophily on ITO surfaces；Assemble the first layer graphene
Surface contact angle after film is 61.6 °, and substrate surface at this moment is graphene film；Assemble after the amphipathic ruthenium complex film of the second layer
Surface contact angle be 51.9 °, improve surface hydrophilicity because the hydrophobic group in amphipathic ruthenium complex be fixed to stone
Black alkene surface, hydrophilic group is exposed on surface, show the substrate surface after the amphipathic ruthenium complex molecular film of assembling hydrophilic
Property；Continue to assemble after film layer, the contact angle of substrate surface slightly about changes at substantially 51 °, as shown in Figure 3.
The electrochemical property test for the substrate through compound function after film modified that the present embodiment is prepared：After modification
Substrate be anode, using cyclic voltammetry judge to after modification substrate carry out cyclic voltammetric test.Test instrument
The AL660-C electrochemical analysers produced for BAS companies of the U.S., parameter setting is as follows：Initial potential is 0 V；High potential is
1.2V；Low potential is 0 V；Scanning at initial stage is Poaitive；Scanning times are 6 times；Stand-by period is 3~5 s；Sensitivity is selected
For 10 μ A；Filtering parameter is 50 Hz；Multiplication factor 1；Sweep speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1 MTBAPF in continuous mode6Solution（Solvent is anhydrous MeCN）As electrolyte, make
With 3h is preceding dried under vacuum, the substrate after modification is used as working electrode, Ag/AgNO3As reference electrode, Pt lines are as a comparison
Electrode.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential correction.After being modified
The voltammogram of substrate is as shown in Figure 4.According to formula（1）With（2）Calculating obtains graphene-based after film modified through 5 layers of compound function
The quantity of electric charge on bottom is 6.979 × 10-6 C, amount of coating is 1.394 × 10-10 mol/cm2。
Embodiment 3：Graphene-based compound functional film material, is that the pyrenyl in amphipathic ruthenium complex molecule passes through non-co-
The effect of valence link is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxychlorination
In zirconium solution and symmetry ruthenium complex solution, amphipathic ruthenium complex molecule and symmetry ruthenium complex are divided by zirconium ion
Connected between son, and symmetry ruthenium complex molecule, the number of plies and the adjustable composite film material of thickness are obtained, wherein amphipathic ruthenium
The chemical formula of complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
。
The preparation method of the graphene-based compound functional film material, it is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 11,3.238mg amphipathic ruthenium complex [Ru (Py are weighed2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water, uses
HCl is adjusted after PH to 6, addition ultra-pure water to 25ml, produces 50 μM of ruthenium complex solution；
（2）The preparation of zirconyl chloride solution：30ml ultra-pure waters are added in clean beaker, 193.2mg oxychlorination is weighed
Zirconium is dissolved in ultra-pure water solution, and 20mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 11,2.864mg ruthenium complexes [Ru (XPOH) is weighed2](PF6)2It is dissolved in solution, is adjusted with HCl after PH to 6, is added super
Pure water produces 50 μM of symmetry ruthenium complex solution to 25ml；
（4）The preparation of graphene dispersing solution：By 0.2g lauryl sodium sulfate（SDS）It is dissolved in 10ml water and obtains 2%
（w/v）The SDS aqueous solution, by 2.5mg graphenes（Graphene, -325mesh）It is dispersed in the 10ml SDS aqueous solution, ultrasound
Moved to after ripple decentralized processing 1.5h in centrifuge, 3h is centrifuged under 15krpm rotating speeds, remove bottom residues, obtaining concentration is
0.15mg/ml graphene dispersing solution；
（5）The hydrophilic treated of ITO conductive glass surfaces：By NH3、H2O21 is pressed with ultra-pure water:1:5 volume ratio mixed preparing
RCA solution, ITO substrates are immersed in RCA solution and just faced outwardly, and slight shake away is moved in water-bath after bubble, 90
DEG C heating 2h after take out ITO substrates with ultra-pure water clean, nitrogen drying；
（6）The preparation at graphene-based bottom：By step（5）In surface hydrophilic processing after ITO substrates be fixed on rotation Tu
On instrument, step is added dropwise（4）The middle graphene dispersing solution configured, the spin coating instrument low rate start stage speed of rotation is 200rpm, when
Between be 3s, high speed rotation rate is 1000rpm, and the time is 70s, graphene dispersing solution is uniformly sprawled film forming, and room temperature, which is placed, to be made
Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with nitrogen dry up obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in just face outwardly, slight concussion removes bubble, impregnates at room temperature after 12h
Take out ITO substrates and clean nitrogen drying with ultra-pure water；
（8）The assembling of symmetry ruthenium complex molecular film：By step（8）Obtained ITO substrates are immersed in step（2）In
Zirconyl chloride solution, takes out substrate ultra-pure water after 3h after impregnating at room temperature and cleans nitrogen drying, be then immersed in being immersed in step
Suddenly（3）In symmetry ruthenium complex solution in, slight concussion removes bubble, impregnates ITO substrates are taken out after 6h at room temperature, use
Ultra-pure water cleans nitrogen drying；
（9）Repeat step（8）, the compound functional membrane that the number of plies is 6 layers is obtained, wherein the 1st layer is graphene film, the 2nd layer
For amphipathic ruthenium complex molecular film, the 3rd, 4,5,6 layers be symmetry ruthenium complex molecular film.
The surface contact angle test for the compound functional membrane that the present embodiment is prepared：The ITO bases of surface hydrophilic before processing
The contact angle on piece surface is 87.2 °, and it is hydrophobicity to illustrate cleaning ITO surfaces；ITO substrate surfaces after surface hydrophilic processing connect
Feeler is 65.3 °, it was demonstrated that the hydrophilic treatment method of the present invention improves the hydrophily on ITO surfaces；Assemble the first layer graphene
Surface contact angle after film is 60.4 °, and substrate surface at this moment is graphene film；Assemble after the amphipathic ruthenium complex film of the second layer
Surface contact angle be 53.6 °, improve surface hydrophilicity because the hydrophobic group in amphipathic ruthenium complex be fixed to stone
Black alkene surface, hydrophilic group is exposed on surface, show the substrate surface after the amphipathic ruthenium complex molecular film of assembling hydrophilic
Property；Continue to assemble after film layer, the contact angle of substrate surface slightly about changes at substantially 52 °, as shown in Figure 5.
The electrochemical property test for the substrate through compound function after film modified that the present embodiment is prepared：After modification
Substrate be anode, using cyclic voltammetry judge to after modification substrate carry out cyclic voltammetric test.Test instrument
The AL660-C electrochemical analysers produced for BAS companies of the U.S., parameter setting is as follows：Initial potential is 0 V；High potential is
1.2V；Low potential is 0 V；Scanning at initial stage is Poaitive；Scanning times are 6 times；Stand-by period is 3~5 s；Sensitivity is selected
For 10 μ A；Filtering parameter is 50 Hz；Multiplication factor 1；Sweep speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1 MTBAPF in continuous mode6Solution（Solvent is anhydrous MeCN）As electrolyte, make
With 3h is preceding dried under vacuum, the substrate after modification is used as working electrode, Ag/AgNO3As reference electrode, Pt lines are as a comparison
Electrode.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential correction.After being modified
The voltammogram of substrate is as shown in Figure 6.According to formula（1）With（2）Calculating obtains graphene-based after film modified through 6 layers of compound function
The quantity of electric charge on bottom is 8.133 × 10-6 C, amount of coating is 1.621 × 10-10 mol/cm2。
Embodiment 4：Graphene-based compound functional film material, is that the pyrenyl in amphipathic ruthenium complex molecule passes through non-co-
The effect of valence link is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxychlorination
In zirconium solution and symmetry ruthenium complex solution, amphipathic ruthenium complex molecule and symmetry ruthenium complex are divided by zirconium ion
Connected between son, and symmetry ruthenium complex molecule, the number of plies and the adjustable composite film material of thickness are obtained, wherein amphipathic ruthenium
The chemical formula of complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
。
The preparation method of the graphene-based compound functional film material, it is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 11,0.648mg amphipathic ruthenium complex [Ru (Py are weighed2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water, uses
HCl is adjusted after PH to 6, addition ultra-pure water to 25ml, produces 10 μM of ruthenium complex solution；
（2）The preparation of zirconyl chloride solution：30ml ultra-pure waters are added in clean beaker, 96.6mg zirconium oxychlorides are weighed
It is dissolved in ultra-pure water solution, 10mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 11,0.573mg ruthenium complexes [Ru (XPOH) is weighed2](PF6)2It is dissolved in solution, is adjusted with HCl after PH to 6, is added super
Pure water produces 10 μM of symmetry ruthenium complex solution to 25ml；
（4）The preparation of graphene dispersing solution：By 0.2g lauryl sodium sulfate（SDS）It is dissolved in 10ml water and obtains 2%
（w/v）The SDS aqueous solution, by 2.5mg graphenes（Graphene, -325mesh）It is dispersed in the 10ml SDS aqueous solution, ultrasound
Moved to after ripple decentralized processing 1.5h in centrifuge, 3h is centrifuged under 15krpm rotating speeds, remove bottom residues, obtaining concentration is
0.15mg/ml graphene dispersing solution；
（5）The hydrophilic treated of ITO conductive glass surfaces：By NH3、H2O21 is pressed with ultra-pure water:1:5 volume ratio mixed preparing
RCA solution, ITO substrates are immersed in RCA solution and just faced outwardly, and slight shake away is moved in water-bath after bubble, 90
DEG C heating 2h after take out ITO substrates with ultra-pure water clean, nitrogen drying；
（6）The preparation at graphene-based bottom：By step（5）In surface hydrophilic processing after ITO substrates be fixed on rotation Tu
On instrument, step is added dropwise（4）The middle graphene dispersing solution configured, the spin coating instrument low rate start stage speed of rotation is 200rpm, when
Between be 3s, high speed rotation rate is 1000rpm, and the time is 70s, graphene dispersing solution is uniformly sprawled film forming, and room temperature, which is placed, to be made
Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with nitrogen dry up obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in just face outwardly, slight concussion removes bubble, impregnates at room temperature after 12h
Take out ITO substrates and clean nitrogen drying with ultra-pure water；
（8）The assembling of symmetry ruthenium complex molecular film：By step（8）Obtained ITO substrates are immersed in step（2）In
Zirconyl chloride solution, takes out substrate ultra-pure water after 3h after impregnating at room temperature and cleans nitrogen drying, be then immersed in being immersed in step
Suddenly（3）In symmetry ruthenium complex solution in, slight concussion removes bubble, impregnates ITO substrates are taken out after 6h at room temperature, use
Ultra-pure water cleans nitrogen drying；
（9）Repeat step（8）, the compound functional membrane that the number of plies is 6 layers is obtained, wherein the 1st layer is graphene film, the 2nd layer
For amphipathic ruthenium complex molecular film, the 3rd, 4,5,6 layers be symmetry ruthenium complex molecular film.
The surface contact angle test for the compound functional membrane that the present embodiment is prepared：The ITO bases of surface hydrophilic before processing
The contact angle on piece surface is 86.7 °, and it is hydrophobicity to illustrate cleaning ITO surfaces；ITO substrate surfaces after surface hydrophilic processing connect
Feeler is 66.1 °, it was demonstrated that the hydrophilic treatment method of the present invention improves the hydrophily on ITO surfaces；Assemble the first layer graphene
Surface contact angle after film is 61.1 °, and substrate surface at this moment is graphene film；Assemble after the amphipathic ruthenium complex film of the second layer
Surface contact angle be 52.4 °, improve surface hydrophilicity because the hydrophobic group in amphipathic ruthenium complex be fixed to stone
Black alkene surface, hydrophilic group is exposed on surface, show the substrate surface after the amphipathic ruthenium complex molecular film of assembling hydrophilic
Property；Continue to assemble after film layer, the contact angle of substrate surface slightly about changes at substantially 52 °.
The electrochemical property test for the substrate through compound function after film modified that the present embodiment is prepared：After modification
Substrate be anode, using cyclic voltammetry judge to after modification substrate carry out cyclic voltammetric test.Test instrument
The AL660-C electrochemical analysers produced for BAS companies of the U.S., parameter setting is as follows：Initial potential is 0 V；High potential is
1.2V；Low potential is 0 V；Scanning at initial stage is Poaitive；Scanning times are 6 times；Stand-by period is 3~5 s；Sensitivity is selected
For 10 μ A；Filtering parameter is 50 Hz；Multiplication factor 1；Sweep speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1 MTBAPF in continuous mode6Solution（Solvent is anhydrous MeCN）As electrolyte, make
With 3h is preceding dried under vacuum, the substrate after modification is used as working electrode, Ag/AgNO3As reference electrode, Pt lines are as a comparison
Electrode.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential correction.According to formula（1）With
（2）Calculate and obtain through the quantity of electric charge on graphene-based bottom of the 6 layers of compound function after film modified being 3.469 × 10-6 C, amount of coating
It is 0.691 × 10-10 mol/cm2。
Embodiment 5：Graphene-based compound functional film material, is that the pyrenyl in amphipathic ruthenium complex molecule passes through non-co-
The effect of valence link is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxychlorination
In zirconium solution and symmetry ruthenium complex solution, amphipathic ruthenium complex molecule and symmetry ruthenium complex are divided by zirconium ion
Connected between son, and symmetry ruthenium complex molecule, the number of plies and the adjustable composite film material of thickness are obtained, wherein amphipathic ruthenium
The chemical formula of complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
。
The preparation method of the graphene-based compound functional film material, it is comprised the following steps that：
（1）The preparation of amphipathic ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, pH is modulated with ammoniacal liquor
To 11,6.476mg amphipathic ruthenium complex [Ru (Py are weighed2G1MeBip)(XPOH)](PF6)2It is dissolved in ultra-pure water, uses
HCl is adjusted after pH to 6, addition ultra-pure water to 25ml, produces 100 μM of ruthenium complex solution；
（2）The preparation of zirconyl chloride solution：30ml ultra-pure waters are added in clean beaker, 289.8mg oxychlorination is weighed
Zirconium is dissolved in ultra-pure water solution, and 30mM zirconyl chloride solution is made；
（3）The preparation of symmetry ruthenium complex solution：15ml ultra-pure waters are added in clean beaker, PH is modulated with ammoniacal liquor
To 11,5.728mg ruthenium complexes [Ru (XPOH) is weighed2](PF6)2It is dissolved in solution, is adjusted with HCl after PH to 6, is added super
Pure water produces 100 μM of symmetry ruthenium complex solution to 25ml；
（4）The preparation of graphene dispersing solution：By 0.2g lauryl sodium sulfate（SDS）It is dissolved in 10ml water and obtains 2%
（w/v）The SDS aqueous solution, by 2.5mg graphenes（Graphene, -325mesh）It is dispersed in the 10ml SDS aqueous solution, ultrasound
Moved to after ripple decentralized processing 1.5h in centrifuge, 3h is centrifuged under 15krpm rotating speeds, remove bottom residues, obtaining concentration is
0.15mg/ml graphene dispersing solution；
（5）The hydrophilic treated of ITO conductive glass surfaces：By NH3、H2O21 is pressed with ultra-pure water:1:5 volume ratio mixed preparing
RCA solution, ITO substrates are immersed in RCA solution and just faced outwardly, and slight shake away is moved in water-bath after bubble, 90
DEG C heating 2h after take out ITO substrates with ultra-pure water clean, nitrogen drying；
（6）The preparation at graphene-based bottom：By step（5）In surface hydrophilic processing after ITO substrates be fixed on rotation Tu
On instrument, step is added dropwise（4）The middle graphene dispersing solution configured, the spin coating instrument low rate start stage speed of rotation is 200rpm, when
Between be 3s, high speed rotation rate is 1000rpm, and the time is 70s, graphene dispersing solution is uniformly sprawled film forming, and room temperature, which is placed, to be made
Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with nitrogen dry up obtain graphene-based bottom；
（7）The assembling of amphipathic ruthenium complex molecular film on graphene-based bottom：By step（6）In graphene-based bottom submergence
In step（1）In amphipathic ruthenium complex solution in just face outwardly, slight concussion removes bubble, impregnates at room temperature after 12h
Take out ITO substrates and clean nitrogen drying with ultra-pure water；
（8）The assembling of symmetry ruthenium complex molecular film：By step（8）Obtained ITO substrates are immersed in step（2）In
Zirconyl chloride solution, takes out substrate ultra-pure water after 3h after impregnating at room temperature and cleans nitrogen drying, be then immersed in being immersed in step
Suddenly（3）In symmetry ruthenium complex solution in, slight concussion removes bubble, impregnates ITO substrates are taken out after 6h at room temperature, use
Ultra-pure water cleans nitrogen drying；
（9）Repeat step（8）, the compound functional film material that the number of plies is 6 layers is obtained, wherein the 1st layer is graphene film, the
2 layers are amphipathic ruthenium complex molecular film, the 3rd, 4,5,6 layers be symmetry ruthenium complex molecular film.
The surface contact angle test for the compound functional membrane that the present embodiment is prepared：The ITO bases of surface hydrophilic before processing
The contact angle on piece surface is 87.1 °, and it is hydrophobicity to illustrate cleaning ITO surfaces；ITO substrate surfaces after surface hydrophilic processing connect
Feeler is 65.9 °, it was demonstrated that the hydrophilic treatment method of the present invention improves the hydrophily on ITO surfaces；Assemble the first layer graphene
Surface contact angle after film is 60.7 °, and substrate surface at this moment is graphene film；Assemble after the amphipathic ruthenium complex film of the second layer
Surface contact angle be 52.6 °, improve surface hydrophilicity because the hydrophobic group in amphipathic ruthenium complex be fixed to stone
Black alkene surface, hydrophilic group is exposed on surface, show the substrate surface after the amphipathic ruthenium complex molecular film of assembling hydrophilic
Property；Continue to assemble after film layer, the contact angle of substrate surface slightly about changes at substantially 52 °.
The electrochemical property test for the substrate through compound function after film modified that the present embodiment is prepared：After modification
Substrate be anode, using cyclic voltammetry judge to after modification substrate carry out cyclic voltammetric test.Test instrument
The AL660-C electrochemical analysers produced for BAS companies of the U.S., parameter setting is as follows：Initial potential is 0 V；High potential is
1.2V；Low potential is 0 V；Scanning at initial stage is Poaitive；Scanning times are 6 times；Stand-by period is 3~5 s；Sensitivity is selected
For 10 μ A；Filtering parameter is 50 Hz；Multiplication factor 1；Sweep speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1 MTBAPF in continuous mode6Solution（Solvent is anhydrous MeCN）As electrolyte, make
With 3h is preceding dried under vacuum, the substrate after modification is used as working electrode, Ag/AgNO3As reference electrode, Pt lines are as a comparison
Electrode.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential correction.According to formula（1）With
（2）Calculate and obtain through the quantity of electric charge on graphene-based bottom of the 6 layers of compound function after film modified being 4.998 × 10-5 C, amount of coating
It is 9.962 × 10-10 mol/cm2。
The embodiment to the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula, in the knowledge that those of ordinary skill in the art possess, can also make on the premise of present inventive concept is not departed from
Go out various change.
Claims (5)
1. a kind of graphene-based compound functional film material, it is characterised in that：Pyrenyl in amphipathic ruthenium complex molecule passes through
The effect of non-covalent bond is self-assembled on graphene-based bottom, and the graphene-based bottom after self assembly then is repeated into alternating impregnating in oxygen
In chlorination zirconium solution and symmetry ruthenium complex solution, amphipathic ruthenium complex molecule and symmetry ruthenium are coordinated by zirconium ion
Connected between thing molecule, and symmetry ruthenium complex molecule, obtain the number of plies and the adjustable composite film material of thickness, wherein amphiphilic
The chemical formula of property ruthenium complex is as follows：
；
The chemical formula of symmetry ruthenium complex is as follows：
；
The preparation method of above-mentioned graphene-based compound functional film material is as follows：
（1）Ultra-pure water is added in clean container, pH is modulated to 10 ~ 12 with ammoniacal liquor, weighs amphipathic ruthenium complex and be dissolved in
In ultra-pure water, adjusted with HCl after pH to 5 ~ 6,10 ~ 100 μM of amphipathic ruthenium complex solution is made；
（2）Weigh zirconium oxychloride to be dissolved in ultra-pure water solution, 10 ~ 30mM zirconyl chloride solution is made；
（3）Ultra-pure water is added in clean container, pH is modulated to 10 ~ 12 with ammoniacal liquor, weighs symmetry ruthenium complex and be dissolved in
In ultra-pure water, adjusted with HCl after pH to 5 ~ 6,10 ~ 100 μM of symmetry ruthenium complex solution is made；
（4）Lauryl sodium sulfate is dissolved in the water the SDS aqueous solution for obtaining that mass volume ratio is 2%, and graphene dispersion is existed
In the SDS aqueous solution, the volume ratio of the wherein quality of graphene and the SDS aqueous solution is 2:10~4:10, after ultrasonic wave decentralized processing from
The heart is separated off bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/ml；
（5）The hydrophilic treated of ITO conductive glass surfaces：RCA solution is prepared, ITO substrates are immersed in RCA solution, slight shake
Moved to after swinging removing bubble in water-bath, take out ITO substrates after 0.5 ~ 2h of heating and cleaned with ultra-pure water, inert gas drying；
（6）By step（5）Obtained ITO substrates are fixed on rotation Tu instrument, and step is added dropwise（4）The middle graphene dispersion configured
Liquid, starting spin coating instrument makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, and room temperature, which is placed, spontaneously dries it, uses first
Alcohol cleaning substrate, which removes to be dried up with inert gas after SDS surfactants, obtains graphene-based bottom；
（7）By step（6）In graphene-based bottom be immersed in step（1）In amphipathic ruthenium complex solution in, slight concussion
Bubble is removed, taking-up substrate after 6 ~ 12h is impregnated at room temperature rear inert gas drying is cleaned up with ultra-pure water；
（8）By step（7）Obtained substrate is immersed in step（2）In zirconyl chloride solution, at room temperature impregnate 1.5 ~ 3.5h
Substrate ultra-pure water is taken out afterwards and cleans inert gas drying, is then immersed in step（3）In symmetry ruthenium complex solution in, gently
Removing bubble is swung in microseism, and substrate is taken out after impregnating 3 ~ 6h at room temperature, and cleaning inert gas with ultra-pure water dries up；
（9）Repeat step（8）, obtain the number of plies and the adjustable graphene-based compound functional membrane of thickness.
2. the preparation method of the graphene-based compound functional film material described in claim 1, it is characterised in that specific steps are such as
Under：
（1）Ultra-pure water is added in clean container, pH is modulated to 10 ~ 12 with ammoniacal liquor, weighs amphipathic ruthenium complex and be dissolved in
In ultra-pure water, adjusted with HCl after pH to 5 ~ 6,10 ~ 100 μM of amphipathic ruthenium complex solution is made；
（2）Weigh zirconium oxychloride to be dissolved in ultra-pure water solution, 10 ~ 30mM zirconyl chloride solution is made；
（3）Ultra-pure water is added in clean container, pH is modulated to 10 ~ 12 with ammoniacal liquor, weighs symmetry ruthenium complex and be dissolved in
In ultra-pure water, adjusted with HCl after pH to 5 ~ 6,10 ~ 100 μM of symmetry ruthenium complex solution is made；
（4）Lauryl sodium sulfate is dissolved in the water the SDS aqueous solution for obtaining that mass volume ratio is 2%, and graphene dispersion is existed
In the SDS aqueous solution, the volume ratio of the wherein quality of graphene and the SDS aqueous solution is 2:10~4:10, after ultrasonic wave decentralized processing from
The heart is separated off bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/ml；
（5）The hydrophilic treated of ITO conductive glass surfaces：RCA solution is prepared, ITO substrates are immersed in RCA solution, slight shake
Moved to after swinging removing bubble in water-bath, take out ITO substrates after 0.5 ~ 2h of heating and cleaned with ultra-pure water, inert gas drying；
（6）By step（5）Obtained ITO substrates are fixed on rotation Tu instrument, and step is added dropwise（4）The middle graphene dispersion configured
Liquid, starting spin coating instrument makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, and room temperature, which is placed, spontaneously dries it, uses first
Alcohol cleaning substrate, which removes to be dried up with inert gas after SDS surfactants, obtains graphene-based bottom；
（7）By step（6）In graphene-based bottom be immersed in step（1）In amphipathic ruthenium complex solution in, slight concussion
Bubble is removed, taking-up substrate after 6 ~ 12h is impregnated at room temperature rear inert gas drying is cleaned up with ultra-pure water；
（8）By step（7）Obtained substrate is immersed in step（2）In zirconyl chloride solution, at room temperature impregnate 1.5 ~ 3.5h
Substrate ultra-pure water is taken out afterwards and cleans inert gas drying, is then immersed in step（3）In symmetry ruthenium complex solution in, gently
Removing bubble is swung in microseism, and substrate is taken out after impregnating 3 ~ 6h at room temperature, and cleaning inert gas with ultra-pure water dries up；
（9）Repeat step（8）, obtain the number of plies and the adjustable graphene-based compound functional membrane of thickness.
3. the preparation method of graphene-based compound functional film material according to claim 2, it is characterised in that：The step
Suddenly（4）The middle ultrasonic wave decentralized processing time is 0.5 ~ 1.5h, and the ultrasonically treated rear centrifugation time is 1 ~ 3h, and rotating speed is
15krpm。
4. the preparation method of graphene-based compound functional film material according to claim 2, it is characterised in that：Step
（5）In RCA solution be ammoniacal liquor, H2O2With ultra-pure water by volume 1:1:Water-bath in the solution that 5 ratio is obtained by mixing, preparation
Heating-up temperature is 90 DEG C.
5. the preparation method of graphene-based compound functional film material according to claim 2, it is characterised in that：The step
Suddenly（6）In, the low rate start stage speed of rotation of spin coating instrument is 200rpm, and the time is 1 ~ 3s, high speed rotation rate is 700 ~
1000rpm, the time is 70 ~ 120s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410841639.2A CN104681282B (en) | 2014-12-30 | 2014-12-30 | A kind of graphene-based compound functional film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410841639.2A CN104681282B (en) | 2014-12-30 | 2014-12-30 | A kind of graphene-based compound functional film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104681282A CN104681282A (en) | 2015-06-03 |
| CN104681282B true CN104681282B (en) | 2017-08-25 |
Family
ID=53316197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410841639.2A Active CN104681282B (en) | 2014-12-30 | 2014-12-30 | A kind of graphene-based compound functional film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104681282B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167421B (en) * | 2020-01-16 | 2021-09-17 | 南通纺织丝绸产业技术研究院 | Graphene-loaded polyurethane sponge adsorption material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175729A (en) * | 2011-01-13 | 2011-09-07 | 青岛科技大学 | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer |
-
2014
- 2014-12-30 CN CN201410841639.2A patent/CN104681282B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175729A (en) * | 2011-01-13 | 2011-09-07 | 青岛科技大学 | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer |
Non-Patent Citations (1)
| Title |
|---|
| "Janus-type" Ruthenium Complex Bearing Both Phosphonic Acids and Pyrene Groups for Functionalization of ITO and HOPG Surfaces;Li Yang等;《CHEMISTRY LETTERS》;20141112;第44卷(第2期);第160-162页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104681282A (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Manipulation of charge transport in ferroelectric-semiconductor hybrid for photoelectrochemical applications | |
| CN103665409B (en) | A kind of preparation method of the poly- 3,4- ethylenedioxy thiophenes composite membrane of conduction | |
| Chi et al. | A shape-and morphology-controlled metal organic framework template for high-efficiency solid-state dye-sensitized solar cells | |
| Dewalque et al. | TiO 2 multilayer thick films (up to 4 µm) with ordered mesoporosity: influence of template on the film mesostructure and use as high efficiency photoelectrode in DSSCs | |
| Cai et al. | High efficiency over 20% of perovskite solar cells by spray coating via a simple process | |
| KR20130122429A (en) | Hybrid electrode using ag nanowire and graphene and manufacturing method of the same | |
| Chaudhari et al. | Electrochromic thin films of Zn-based MOF-74 nanocrystals facilely grown on flexible conducting substrates at room temperature | |
| CN107093669B (en) | A kind of perovskite solar cell light absorption layer | |
| Zhang et al. | Antisolvent-derived intermediate phases for low-temperature flexible perovskite solar cells | |
| TW201101556A (en) | Method and device for dye adsorption for photosensitizing dye, process and apparatus for producing dye-sensitized solar cell, and dye-sensitized solar cell | |
| Giannopoulos et al. | An alternative methodology for anchoring organic sensitizers onto TiO 2 semiconductors for photoelectrochemical applications | |
| JP6520349B2 (en) | Photoelectric conversion element | |
| Chen et al. | Photoelectrochemical properties of electrostatically self-assembled multilayer films formed by a cobalt complex and graphene oxide | |
| Aji et al. | Ambient processing of methylammonium lead iodide perovskite solar cells via magnetic field-assisted electrodeposition of the precursor film | |
| CN104681282B (en) | A kind of graphene-based compound functional film material and preparation method thereof | |
| JP2007179766A (en) | Dye-sensitized solar cell | |
| Yu et al. | Electrochemical deposition of ZnO porous nanoplate network for Dye-Sensitized solar cells | |
| CN104587847B (en) | A kind of electrical functions film and preparation method thereof | |
| Nasr-Esfahani et al. | Fabrication and characterization of a new dye sensitized solar cell with a new Schiff base cobalt complex as a redox mediator | |
| CN104599847B (en) | A kind of composite film material with electro-chemical activity and preparation method thereof | |
| CN101949026A (en) | Method for preparing perylene polyimide derivative film | |
| CN104576072B (en) | A kind of high electrochemical performance composite membrane and preparation method thereof | |
| CN104589725B (en) | A kind of Graphene-ruthenium complex multilayer complex films and the method preparing Graphene-ruthenium complex multilayer complex films | |
| CN104616895B (en) | A kind of ruthenium complex monomolecular film and the method that self assembly ruthenium complex prepares monomolecular film on graphene | |
| CN104445143A (en) | Method for preparing monomolecular film by assembling graphene on amphiphilic ruthenium complex by using spin-coating process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |