CN104616895B - A kind of ruthenium complex monomolecular film and the method that self assembly ruthenium complex prepares monomolecular film on graphene - Google Patents

A kind of ruthenium complex monomolecular film and the method that self assembly ruthenium complex prepares monomolecular film on graphene Download PDF

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CN104616895B
CN104616895B CN201410838521.4A CN201410838521A CN104616895B CN 104616895 B CN104616895 B CN 104616895B CN 201410838521 A CN201410838521 A CN 201410838521A CN 104616895 B CN104616895 B CN 104616895B
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graphene
ruthenium complex
monomolecular film
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film
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CN104616895A (en
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王�华
杨丽
李孔斋
魏永刚
祝星
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Kunming University of Science and Technology
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Abstract

A kind of method that self assembly ruthenium complex prepares monomolecular film the present invention relates to ruthenium complex monomolecular film and on graphene, belongs to molecular self-assembling technical field of chemistry.This orients the ruthenium complex monomolecular film of self assembly on graphene, pyrenyl in the ruthenium complex monomolecular film in ruthenium complex is interacted with the graphene with pi-electron environment by π π, and two pyrenyls of ruthenium complex molecule are fixed on into graphene interface.Ruthenium complex solution is prepared first, prepare graphene dispersing solution, then the ITO substrates of pretreatment are fixed on rotation Tu instrument, uniformly will sprawl into the graphene-based bottom of film preparation on the graphene dispersing solution substrate configured, finally NW-TFT ruthenium complex prepares monomolecular film on graphene-based bottom.Film prepared by the present invention has good mechanically and chemically stability, many advantages, such as thickness of film is controllable.

Description

A kind of ruthenium complex monomolecular film and the self assembly ruthenium complex preparation list on graphene The method of molecular film
Technical field
The present invention relates to a kind of ruthenium complex monomolecular film and on graphene, self assembly ruthenium complex prepares monomolecular film Method, belong to molecular self-assembling technical field of chemistry.
Background technology
In recent years self-assembling technique because its have the advantages that deposition process and membrane structure molecular level control increasingly by wide General attention.Unimolecular layer membrane self-assembling technique is to be diffused into by the molecule in solution on the substrate of immersion in the solution, is made They occur physical absorption or chemical action, form orderly molecular assembled system.Self assembly prepares the technology of ultrathin membrane, can use In self assembly conducting film, if any assembling film of polyaniline and poly- thiophene phenol etc.;It can also be used for the preparation of electroluminescent device, such as surface The CdSe particles of negativity are assembled with the precursor of polyphenylacetylene (PPV), nano level PPV/CdSe films are obtained, with Electroluminescence Matter.In addition, with the high molecular self-assembled film of diazo, the weak bond between light, heat treatment caudacoria is changed into covalent bond, also can obtain Film that is stable to polar solvent, can be used in determining the functions such as optical-electronic conversion.
Ruthenium is easily formed the complex of hexa-coordinate and variation of valence itself is abundant, and its dissolubility is good, stability is good, oxidation is gone back Former current potential makes it possess excellent electrochemical luminescence performance than the compatibility that relatively low, high electrochemical luminescence efficiency is become reconciled.Ruthenium is matched somebody with somebody Compound thermodynamic stability is good, photochemical light physical message abundant, the active high and long lifespan of excited state reaction and luminescent properties are good It is good.Therefore it is widely used in chemiluminescence at present, and electro transfer, nonlinear optical material, molecular light switch, molecule is known Not, the research in the field such as sensor.
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, the two-dimensional material of only one of which carbon atom thickness.Stone Black alkene is most thin, the most hard nano material in known world, and it is almost fully transparent, and thermal conductivity factor is up to 5300W/ MK, higher than CNT and diamond, its electron mobility is more than 15000cm under normal temperature2/ Vs, and than CNT or silicon wafer Body is high, and resistivity about 10-8 Ω cm, lower than copper or silver, is the minimum material of world resistivity.Because its resistivity is extremely low, The speed of electron transfer is exceedingly fast, therefore is expected to can be used to develop thinner, conductive speed electronic component or crystalline substance of new generation faster Body pipe.Because graphene is substantially a kind of transparent, good conductor, it also is adapted for for manufacturing transparent touch screen, tabula rasa, very To being solar cell.
It is domestic at present on graphene the applicable research of the method and its photo electric of self-assembled monolayer yet there are no Report.The self-assembling method of disclosed molecular film mainly has:
" molecule self-assembly monolayer film/ganister sand adsorption agent disclosed in the A of Publication No. CN 101185879 Chinese patent Preparation method and applications " in, using quartz sand as matrix, with using HNO after organic solvent supersound washing3It is surface-treated, It is placed in afterwards after oven drying and enters (Y) Si (CH2)nAssemble monofilm in-X benzole soln, after through H2O2H after oxidation2SO4Place Reason obtains the molecular film with adsorptivity.
" a kind of long-range orderly layered self-assembled nano structures surpass disclosed in Publication No. CN103028739A Chinese patent In the preparation method of lattice copper ", anion surfactant dodecyl sodium sulfate is used for template, in alcohol-water or second Prepared in two alcohol-water systems with circumfluence method high-sequential, spatial symmetry is high, better crystallinity degree copper nanostructured is super brilliant Product long-range order self-assembled nano structures superlattice copper obtained by lattice, this method is stratiform polycrystal powder.
" prepared by a kind of liquid phase self-assembling technique have dielectricity disclosed in Publication No. CN102583569A Chinese patent In the method for the bismuth ferrite thin film of energy ", with Bi (NO3)3·5H2O、Fe(NO3)3·9H2O is that raw material is dissolved in distilled water, with ice Acetic acid adjusts solution ph, using citric acid as complexing agent, using functionalization self-assembled monolayer as template, by functional substrateization one side Solution surface being suspended in down film being prepared by reverse adsorption, organics removal is incubated after 300 DEG C in drying at room temperature, 550 DEG C of insulation annealings prepare the bismuth ferrite function film of crystallization, afterwards ultraviolet irradiation again, reverse adsorption, dry and simultaneously anneal Processing.It is such repeated multiple times until preparing the bismuth ferrite function film with dielectric properties.
At present, the monomolecular film self-assembly method of complex be it is a kind of be conducive to controlling package assembly and form have efficacious prescriptions Method, can spontaneously form the monolayer of high-sequential by covalent bond or non-covalent bond on the surface of electrode.Self-assembled film point Sub- aligned orderly is close, but assembling process is complicated, high to equipment requirement, need to enter in the preferable laboratory of clean, seal OK.Moreover, to make reactant quickly and efficiently be reacted with substrate active part, complex need to have preferable dissolving in a solvent Degree.Thus a kind of orientable, self assembling process of design invention is simple and can form stability height, the molecular film side of favorable repeatability Method is very necessary.
The content of the invention
The problem of existing for above-mentioned prior art and deficiency, the present invention provide one kind self-composed monomolecular on graphene The method of film and its photoelectric properties application.Pyrenyl in the present invention in ruthenium complex molecule and the graphene with π-electronic environment Interacted by π-π, two pyrenyls of ruthenium complex molecule are fixed on graphene interface, so as to realize at graphene-based bottom Upper self assembly ruthenium complex monomolecular film, method of the invention is simple to operate, and modification is uniform abundant, at room temperature using simple appearance Device is operable, without specific condition and equipment, and the substrate after modification has excellent electro-chemical activity, the film tool of preparation There are good mechanically and chemically stability, many advantages, such as thickness of film is controllable.The present invention is achieved through the following technical solutions.
A kind of pyrenyl in ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-electronics The graphene of environment is interacted by π-π, and two pyrenyls of ruthenium complex molecule are fixed on into graphene interface, and the ruthenium coordinates Thing [Ru (Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
The ruthenium complex monomolecular film has good machinery, chemical stability and excellent photoelectric properties.
A kind of method that self assembly ruthenium complex on graphene prepares monomolecular film, it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:Dichloromethane is added in clean container, by ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane solution, ruthenium complex solution is made;
The preparation of step 2, graphene dispersing solution:SDS is dissolved in the water and obtains the SDS aqueous solution, by graphene ultrasound point It is dispersed in the SDS aqueous solution, is centrifuged after ultrasonic wave decentralized processing and remove bottom residues, obtain graphene dispersing solution;
The pretreatment of step 3, ITO substrates:ITO substrates are immersed in RCA solution, slight concussion is moved to after removing bubble Heating water bath is carried out in water-bath, ITO substrates are taken out after heating and are cleaned with ultra-pure water, inert gas drying;
Step 4, the preparation at graphene-based bottom:The ITO substrates pre-processed through step 3 are fixed on rotation Tu instrument, step is added dropwise The graphene dispersing solution configured in rapid 2, starting spin coating instrument makes graphene dispersing solution uniformly sprawl film forming, room on ITO substrates Temperature place spontaneously dry it, with methanol clean substrate remove SDS surfactants after with inert gas dry up obtain graphene Substrate;
Step 5, graphene-based bottom NW-TFT ruthenium complex prepare monomolecular film:The graphene that step 4 is prepared Substrate is immersed in the ruthenium complex solution that step 1 configuration is obtained, and slight concussion removes bubble, is taken out after impregnating at room temperature, The drying of rear inert gas is cleaned up with dichloromethane, that is, prepares ruthenium complex monomolecular film, this is through single point of ruthenium complex The film modified Graphene electrodes of son are used as anode.
In the step 1 concentration of ruthenium complex solution be 50 μM, μM be μm ol/L.
SDS concentration of aqueous solution is 2% in the step 2(w/c), ultrasonic disperse processing time is 0.5 ~ 1.5h, is centrifuged Time is 1 ~ 3h, and rotating speed is 15krpm.
RCA solution is NH in the step 33, H2O21 is pressed with ultra-pure water:1:The solution of 5 volume ratio mixing, heating water bath Temperature is 90 DEG C, and the heating water bath time is 0.5 ~ 2h.
The low rate start stage speed of rotation of spin coating instrument is 150 ~ 200rpm in the step 4, and the time is 3 ~ 5s, is revolved at a high speed Rotational speed rate is 700 ~ 800rpm, and the time is 70 ~ 120s.
Dip time in the step 5 is 10 ~ 24h.
The beneficial effects of the invention are as follows:
1st, the pyrenyl in the two sufficient ruthenium complex molecule is interacted with the graphene with π-electronic environment by π-π, Two pyrenyls of ruthenium complex molecule are fixed on graphene interface, so as to realize that the sufficient ruthenium of self assembly two is matched somebody with somebody on graphene-based bottom Compound monomolecular film, molecular film is firmly combined with graphene-based bottom.
2nd, the sufficient ruthenium complex [Ru (Py of two used in the present invention4G2MeBip2)](PF6)2Have in multi-solvents preferably Solubility, is conducive to complex quickly and efficiently to be reacted with substrate active part, so as to improve efficiency and the self assembly of self assembly The quality of film.
3rd, preparation method of the invention obtains the assembled layers that complex is consolidated on electrode, by with light, electrical property On ruthenium complex molecular self-assembling graphene, being formed has light, the self assembly molecule film of Electricity Functional, and Iy self-assembled layer is in substrate It is evenly distributed, and with good electro-chemical activity and photophysical property.Graphene electrodes after modification are anode, are had Excellent light, chemical property, available for fields such as DSSCs.
4th, the present invention be using simple receptacle at room temperature it is operable, it is whole without complicated instrument and equipment and specific condition The individual membrane process technique that is self-assembled into is easily controllable, simple to operate, and preparation cost is low, and raw material is easy to get, and film forming matter is not by substrate sizes With the limitation of shape, the film of preparation has good mechanically and chemically stability, the thickness and structure-controllable of film, and film forming It is reproducible.
Brief description of the drawings
Fig. 1 is the voltammogram for the ruthenium complex monomolecular film that the embodiment of the present invention 1 is prepared;
Fig. 2 is the sweep speed and current relationship figure for the ruthenium complex monomolecular film that the embodiment of the present invention 1 is prepared;
Fig. 3 is the voltammogram for the ruthenium complex monomolecular film that the embodiment of the present invention 2 is prepared;
Fig. 4 is the sweep speed and current relationship figure for the ruthenium complex monomolecular film that the embodiment of the present invention 2 is prepared;
Fig. 5 is the voltammogram for the ruthenium complex monomolecular film that the embodiment of the present invention 3 is prepared;
Fig. 6 is the sweep speed and current relationship figure for the ruthenium complex monomolecular film that the embodiment of the present invention 3 is prepared.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring The graphene in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into graphene interface, the ruthenium complex [Ru(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
The method that self assembly ruthenium complex prepares monomolecular film on graphene, it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:35ml dichloromethane is added in clean container, 4.046mg rutheniums are matched somebody with somebody Compound [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane solution, ruthenium complex solution is made(Ruthenium complex solution Concentration is 50 μM);
The preparation of step 2, graphene dispersing solution:By 0.4gSDS(Lauryl sodium sulfate)It is dissolved in 20ml water and obtains The SDS aqueous solution((Concentration is 2%(w/c)), by 4mg graphenes(Graphene, -325mesh)Ultrasonic disperse is water-soluble in 20mlSDS In liquid, ultrasonic wave is moved in centrifuge after disperseing 0.5h processing, and 1h is centrifuged under 15krpm rotating speeds and removes bottom residues, is obtained To graphene dispersing solution;
The pretreatment of step 3, ITO substrates:ITO substrates are immersed in RCA solution, slight concussion is moved to after removing bubble 90 DEG C of heating 0.5h of heating water bath are carried out in water-bath, ITO substrates are taken out after heating and are cleaned with ultra-pure water, inert gas drying, Wherein RCA solution is NH3, H2O21 is pressed with ultra-pure water:1:The solution of 5 volume ratio mixing;
Step 4, the preparation at graphene-based bottom:The ITO substrates pre-processed through step 3 are fixed on rotation Tu instrument, step is added dropwise The graphene dispersing solution configured in rapid 2, it is 150rpm to start the spin coating instrument low rate start stage speed of rotation, and the time is 5s, high The fast speed of rotation is 700rpm, and the time is 120s, makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, room temperature is placed Spontaneously dry it, with methanol clean substrate remove SDS surfactants after with inert gas drying obtain graphene-based bottom;
Step 5, graphene-based bottom NW-TFT ruthenium complex prepare monomolecular film:The graphene that step 4 is prepared Substrate is immersed in the ruthenium complex solution that step 1 configuration is obtained, and slight concussion removes bubble, is taken after impregnating 10h at room temperature Go out, rear inert gas drying is cleaned up with dichloromethane, that is, prepares ruthenium complex monomolecular film, this is through ruthenium complex list The film modified electrode of molecule is used as anode.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:This is through ruthenium complex unimolecule Film modified Graphene electrodes judge to carry out the substrate after modification the survey of cyclic voltammetric as anode, using cyclic voltammetry Examination.It is the AL660-C electrochemical analysers that BAS companies of the U.S. produce to test instrument, and parameter setting is as follows:Initial potential is 0V;High potential is 1.2V;Low potential is 0V;Scanning at initial stage is Poaitive;Scanning times are 6 times;Stand-by period is 3~5s; Sensitivity selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep speed (unit is V/s) needs to divide according to experiment It is not set as:0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in continuous mode6Solution(Solvent is anhydrous MeCN)It is used as electricity 3h is dried under vacuum before Xie Zhi, use, the graphene-based bottom after modification is used as working electrode, Ag/AgNO3As with reference to electricity Pole, Pt lines electrode as a comparison.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure carry out current potential benefit Just, the voltammogram obtained is as shown in Figure 1.
Current value increases with the increase of sweep speed as can be seen from Figure 2, anode current ipaWith the letter of scan velocity V Number relation is ipa=5.028×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-6.847×10-6V, nothing By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule has successfully been assembled into graphene-based On bottom.The quantity of electric charge and amount of coating at graphene-based bottom 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)Calculating the quantity of electric charge for the Graphene electrodes for obtaining modifying through ruthenium complex monomolecular film is 1.157×10-6C, amount of coating is 2.306 × 10-11 mol/cm2
Embodiment 2
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring The graphene in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into graphene interface, the ruthenium complex [Ru(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
The method that self assembly ruthenium complex prepares monomolecular film on graphene, it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:30ml dichloromethane is added in clean container, 3.468mg rutheniums are matched somebody with somebody Compound [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane solution, ruthenium complex solution is made(Ruthenium complex solution Concentration is 50 μM);
The preparation of step 2, graphene dispersing solution:By 0.2gSDS(Lauryl sodium sulfate)It is dissolved in 10ml water and obtains The SDS aqueous solution((Concentration is 2%(w/c)), by 2mg graphenes(Graphene, -325mesh)Ultrasonic disperse is water-soluble in 10mlSDS In liquid, ultrasonic wave is moved in centrifuge after disperseing 1.5h processing, and 3h is centrifuged under 15krpm rotating speeds and removes bottom residues, is obtained To graphene dispersing solution;
The pretreatment of step 3, ITO substrates:ITO substrates are immersed in RCA solution, slight concussion is moved to after removing bubble 90 DEG C of heating 2h of heating water bath are carried out in water-bath, ITO substrates are taken out after heating and are cleaned with ultra-pure water, inert gas drying, its Middle RCA solution is NH3, H2O21 is pressed with ultra-pure water:1:The solution of 5 volume ratio mixing;
Step 4, the preparation at graphene-based bottom:The ITO substrates pre-processed through step 3 are fixed on rotation Tu instrument, step is added dropwise The graphene dispersing solution configured in rapid 2, it is 170rpm to start the spin coating instrument low rate start stage speed of rotation, and the time is 4s, high The fast speed of rotation is 800rpm, and the time is 100s, makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, room temperature is placed Spontaneously dry it, with methanol clean substrate remove SDS surfactants after with inert gas drying obtain graphene-based bottom;
Step 5, graphene-based bottom NW-TFT ruthenium complex prepare monomolecular film:The graphene that step 4 is prepared Substrate is immersed in the ruthenium complex solution that step 1 configuration is obtained, and slight concussion removes bubble, is taken after impregnating 15h at room temperature Go out, rear inert gas drying is cleaned up with dichloromethane, that is, prepares ruthenium complex monomolecular film, this is through ruthenium complex list The film modified Graphene electrodes of molecule are used as anode.
The chemical property that self assembly ruthenium complex monomolecular film is oriented on graphene that the present embodiment is prepared is surveyed Examination:The Graphene electrodes modified through ruthenium complex monomolecular film are anode, are judged using cyclic voltammetry to the substrate after modification Carry out the test of cyclic voltammetric.It is the AL660-C electrochemical analysers that BAS companies of the U.S. produce to test instrument, and parameter is set Put as follows:Initial potential is 0V;High potential is 1.2V;Low potential is 0V;Scanning at initial stage is Poaitive;Scanning times are 6 times; Stand-by period is 3~5s;Sensitivity selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep speed (unit be V/ S) it is respectively set as according to experiment needs:0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in continuous mode6Solution(Solvent For anhydrous MeCN)As electrolyte, 3h is dried under vacuum before use, the graphene-based bottom after modification is used as working electrode, Ag/ AgNO3As reference electrode, Pt lines electrode as a comparison.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, is determined Data carry out current potential correction, obtained voltammogram is as shown in Figure 3.
Current value increases with the increase of sweep speed as can be seen from Figure 4, anode current ipaWith the letter of scan velocity V Number relation is ipa=4.681×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-4.872×10-6V, nothing By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule has successfully been assembled into graphene-based On bottom.The quantity of electric charge and amount of coating at graphene-based bottom press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)Calculating the quantity of electric charge for the Graphene electrodes for obtaining modifying through ruthenium complex monomolecular film is 1.149×10-6C, amount of coating is 2.290 × 10-11 mol/cm2
Embodiment 3
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring The graphene in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into graphene interface, the ruthenium complex [Ru(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
The method that self assembly ruthenium complex prepares monomolecular film on graphene, it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:50ml dichloromethane is added in clean container, 5.202mg rutheniums are matched somebody with somebody Compound [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane solution, ruthenium complex solution is made(Ruthenium complex solution Concentration is 50 μM);
The preparation of step 2, graphene dispersing solution:By 0.2gSDS(Lauryl sodium sulfate)It is dissolved in 10ml water and obtains The SDS aqueous solution((Concentration is 2%(w/c)), by 2mg graphenes(Graphene, -325mesh)Ultrasonic disperse is water-soluble in 10mlSDS In liquid, ultrasonic wave is moved in centrifuge after disperseing 1.5h processing, and 3h is centrifuged under 15krpm rotating speeds and removes bottom residues, is obtained To graphene dispersing solution;
The pretreatment of step 3, ITO substrates:ITO substrates are immersed in RCA solution, slight concussion is moved to after removing bubble 90 DEG C of heating 2h of heating water bath are carried out in water-bath, ITO substrates are taken out after heating and are cleaned with ultra-pure water, inert gas drying, its Middle RCA solution is NH3, H2O21 is pressed with ultra-pure water:1:The solution of 5 volume ratio mixing;
Step 4, the preparation at graphene-based bottom:The ITO substrates pre-processed through step 3 are fixed on rotation Tu instrument, step is added dropwise The graphene dispersing solution configured in rapid 2, it is 180rpm to start the spin coating instrument low rate start stage speed of rotation, and the time is 3s, high The fast speed of rotation is 750rpm, and the time is 70s, makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, room temperature, which is placed, to be made Its spontaneously dry, with methanol clean substrate remove SDS surfactants after with inert gas dry up obtain graphene-based bottom;
Step 5, graphene-based bottom NW-TFT ruthenium complex prepare monomolecular film:The graphene that step 4 is prepared Substrate is immersed in the ruthenium complex solution that step 1 configuration is obtained, and slight concussion removes bubble, is taken after impregnating 24h at room temperature Go out, rear inert gas drying is cleaned up with dichloromethane, that is, prepares ruthenium complex monomolecular film, this is through ruthenium complex list The film modified Graphene electrodes of molecule are used as anode.
The electrochemical property test of self assembly ruthenium complex monomolecular film on graphene that the present embodiment is prepared:Through The Graphene electrodes of ruthenium complex monomolecular film modification are anode, judge to follow the substrate after modification using cyclic voltammetry The test of ring volt-ampere.It is the AL660-C electrochemical analysers that BAS companies of the U.S. produce to test instrument, and parameter setting is as follows: Initial potential is 0V;High potential is 1.2V;Low potential is 0V;Scanning at initial stage is Poaitive;Scanning times are 6 times;During wait Between be 3~5s;Sensitivity selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep speed (unit is V/s) basis Experiment needs are respectively set as:0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte, 3h is dried under vacuum before use, the graphene-based bottom after modification is used as working electrode, Ag/AgNO3 As reference electrode, Pt lines electrode as a comparison.20 minutes nitrogen is first passed through before experiment and removes the oxygen in solution, the data of measure Current potential correction is carried out, obtained voltammogram is as shown in Figure 5.
Current value increases with the increase of sweep speed as can be seen from Figure 6, anode current ipaWith the letter of scan velocity V Number relation is ipa=4.569×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-4.430×10-6V, nothing By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule has successfully been assembled into graphene-based On bottom.The quantity of electric charge and amount of coating at graphene-based bottom press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)Calculating the quantity of electric charge for the Graphene electrodes for obtaining modifying through ruthenium complex monomolecular film is 1.150×10-7 C, amount of coating is 2.292 × 10-11 mol/cm2
Above in conjunction with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned Embodiment, can also be before present inventive concept not be departed from the knowledge that those of ordinary skill in the art possess Put that various changes can be made.

Claims (6)

1. a kind of method that self assembly ruthenium complex on graphene prepares monomolecular film, wherein ruthenium in ruthenium complex monomolecular film Pyrenyl in complex is interacted with the graphene with π-electronic environment by π-π, by two pyrenes of ruthenium complex molecule Base is fixed on graphene interface, the ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
,
It is characterized in that comprising the following steps that:
The preparation of step 1, ruthenium complex solution:Dichloromethane is added in clean container, by ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane solution, ruthenium complex solution is made;
The preparation of step 2, graphene dispersing solution:SDS is dissolved in the water and obtains the SDS aqueous solution, graphene ultrasonic disperse is existed Centrifuged in the SDS aqueous solution, after ultrasonic wave decentralized processing and remove bottom residues, obtain graphene dispersing solution;
The pretreatment of step 3, ITO substrates:ITO substrates are immersed in RCA solution, slight concussion moves to water-bath after removing bubble Heating water bath is carried out in pot, ITO substrates are taken out after heating and are cleaned with ultra-pure water, inert gas drying;
Step 4, the preparation at graphene-based bottom:The ITO substrates pre-processed through step 3 are fixed on rotation Tu instrument, are added dropwise in step 2 The graphene dispersing solution configured, starting spin coating instrument makes graphene dispersing solution is uniform on ITO substrates to sprawl film forming, and room temperature is placed Spontaneously dry it, with methanol clean substrate remove SDS surfactants after with inert gas drying obtain graphene-based bottom;
Step 5, graphene-based bottom NW-TFT ruthenium complex prepare monomolecular film:The graphene-based bottom that step 4 is prepared It is immersed in the ruthenium complex solution that step 1 configuration is obtained, slight concussion removes bubble, is taken out after impregnating at room temperature, with two Chloromethanes cleans up rear inert gas drying, that is, prepares ruthenium complex monomolecular film, this is through ruthenium complex monomolecular film The Graphene electrodes of modification are used as anode.
2. the method that the self assembly ruthenium complex according to claim 1 on graphene prepares monomolecular film, its feature exists In:The concentration of ruthenium complex solution is 50 μM in the step 1.
3. the method that the self assembly ruthenium complex according to claim 1 on graphene prepares monomolecular film, its feature exists In:In the step 2 SDS concentration of aqueous solution be 2%, ultrasonic disperse processing time be 0.5 ~ 1.5h, centrifuge the time be 1 ~ 3h, rotating speed is 15krpm.
4. the method that the self assembly ruthenium complex according to claim 1 on graphene prepares monomolecular film, its feature exists In:RCA solution is NH in the step 33, H2O21 is pressed with ultra-pure water:1:The solution of 5 volume ratio mixing, water bath heating temperature For 90 DEG C, the heating water bath time is 0.5 ~ 2h.
5. the method that the self assembly ruthenium complex according to claim 1 on graphene prepares monomolecular film, its feature exists In:The low rate start stage speed of rotation of spin coating instrument is 150 ~ 200rpm in the step 4, and the time is 3 ~ 5s, and speed is rotated at a high speed Rate is 700 ~ 800rpm, and the time is 70 ~ 120s.
6. the method that the self assembly ruthenium complex according to claim 1 on graphene prepares monomolecular film, its feature exists In:Dip time in the step 5 is 10 ~ 24h.
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