CN104589725B - A kind of Graphene-ruthenium complex multilayer complex films and the method preparing Graphene-ruthenium complex multilayer complex films - Google Patents
A kind of Graphene-ruthenium complex multilayer complex films and the method preparing Graphene-ruthenium complex multilayer complex films Download PDFInfo
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Abstract
The present invention relates to a kind of Graphene ruthenium complex multilayer complex films and the method preparing Graphene ruthenium complex multilayer complex films, belong to technical field of composite preparation.Graphene ruthenium complex multilayer complex films is by repeating orderly superposition symmetry ruthenium complex in the monomolecular film of substrate or Graphene forms multilayer complex films, a pair pyrenyl in symmetry ruthenium complex molecule is fixed on HOPG interface with HOPG by non-covalent bond effect, pyrenyl and the Graphene with cancellated pi-electron environment are interacted by another, first tunic is symmetry ruthenium complex, the second layer is Graphene, so repeat, wherein odd number is symmetry ruthenium complex layer, and even number is graphene layer.The present invention compared with single Graphene or ruthenium complex self-assembled film more in a organized way, chemical property significantly improves.
Description
Technical field
The present invention relates to a kind of Graphene-ruthenium complex multilayer complex films and prepare Graphene-ruthenium complex MULTILAYER COMPOSITE
The method of film, belongs to technical field of composite preparation.
Background technology
LBL self-assembly (layer-by-layer self-assembly, LBL) is that the fast development nineties in last century rises
The one surface modification method simple, multi-functional come.LBL initially with charged substrate (substrate) at oppositely charged
In alternating deposit prepare polyelectrolyte self-assembled multilayer film (polyelectrolyte self-assembled
Mulilayers).In the short coming year more than ten, in terms of basic research, LBL has obtained huge development.The raw material that LBL is suitable for is
Polymer brush, inorganic charged nanosize particle,colloid etc. is expanded to by initial classical polyelectrolyte.LBL Applicable media is extended by water
To organic solvent and ionic liquid.The driving force of LBL has electrostatic force to expand to hydrogen bond, halogen atom, coordinate bond, even chemistry
Key.
HOPG(Highly Oriented Pyrolytic Graphite, highly oriented pyrolytic graphite) it is a kind of novel high-purity
Degree carbon, be pyrolytic graphite after high temperature high pressure process prepare a kind of New graphite material, function the most prominent for HOPG is to have one
The surface of individual unusual light and electrical conductance, its surface is almost a graphite linings, the atom of the highly directional orthohexagonal of standard
Order arranges so that the roughness on surface is less than 0.1nm.HOPG has layer structure so that sample preparation is very simple, with one
Bar adhesive tape is bonded on the surface of HOPG, is then torn, and adhesive tape will be stained with the HOPG of thin layer, and it is new for newly splitting top layer
Smooth conductive surface, can serve as sample base material.Owing to HOPG has π-electronic environment, can be mutual by π-π
Effect connects other coordination compounds with π-electronic environment and prepares the molecular film possessing excellent properties.
Graphene (Graphene) is the new material of a kind of monolayer laminated structure being made up of carbon atom.It is a kind of former by carbon
Son is with sp2Hybrid orbital composition hexangle type is the flat film of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.Stone
Ink alkene is the nano material that known world is the thinnest, the hardest, and it is almost fully transparent, for the material that world resistivity is minimum
Material.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, be therefore expected to can be used to develop thinner, conduction speed is faster
A new generation's electronic component or transistor.Due to a kind of transparent, good conductor of Graphene, it also is adapted for for manufacturing
Bright Touch Screen, tabula rasa, even solaode.
The most domestic research to the method at carbon materials surface layer self assembly ruthenium complex/graphene composite film is also
Have no report.The self-assembling method of disclosed molecular film mainly has:
Disclosed " a kind of Graphene/bis-self-assembling peptide the laminated film of the Chinese patent of Publication No. CN 102659918 A
And preparation method thereof " in, dipeptides is dissolved in hexafluoroisopropanol after being configured to solution and mixing with graphene nanometer sheet suspension
Closing, obtain the mixed solution of Graphene/dipeptides, drop coating is to the substrate surface cleaned up afterwards, then puts it into baking oven
In be dried 18 ~ 24 hours, obtain Graphene/bis-self-assembling peptide laminated film.
Disclosed " a kind of layer based on dopamine modification polyelectrolyte of the Chinese patent of Publication No. CN 102634792 A
Layer electrostatic self-assembled method and application " in, by dopamine with the polyelectrolyte with carboxyl by carbodiimide/N-hydroxyl amber
Amber acid imide (EDS/NHS) lucifuge is reacted, and generates the polyelectrolyte that main-chain carboxylic group part is substituted by o-phenol functional group, profit
Formed with the o-phenol two hydroxyls on phenyl ring and material surface and combine closely, and with the polyelectrolyte with opposite charges
Layer-by-layer assembly becomes multilayer film.The method firstly the need of a charged substrate and is carried out under the conditions of lucifuge, whole instead
Need to monitor constantly the pH value of reaction system during Ying.
The Chinese patent of Publication No. CN 1394901 A is disclosed " with electrostatic attraction layer-layer self-assembled modified polyester class material
The method that material has cell compatible biological material for surface " in, first obtain with polyamine amine solution polyester polymer surface
The polymer of surface band free amino, then make polymer surfaces positively charged with acid acidifying, then utilize electrostatic attraction layer-layer from group
The method of dress, alternately assembles single or multiple lift and has bioactive different polyanion and polycation on its surface.The party
Method operates under vacuo.
At present, both at home and abroad for the research work overwhelming majority of layer-by-layer with classical, based on electrostatic phase
L-B (Langmuir-Blodgett) membrane technology of interaction and electrostatic laminated assembling technology are main.Although the degree of order of LB film
Height, compound with regular structure, but the LB film generated is a kind of metastable structure, stablizes heat, chemical environment, time and external pressure
Property poor, the preparation of LB film simultaneously needs expensive film groove and strict substrate.Electrostatic laminated assembling technology is firstly the need of a band
The substrate of electric charge, suprabasil CHARGE DISTRIBUTION and existing way directly affect the structural stability of film, and different materials often needs
Otherwise same substrate pretreatment, hence in so that the simplification of laminated assembling technology and universality are had a greatly reduced quality, in addition to substrate, solution
Concentration, pH, cleaning and adsorption time etc. all can affect Electrostatic Absorption quality.Self-assembly method is that one is conducive to controlling package assembly
With the effective ways of form, self-assembled film molecules align is tight in order, but assembling process is complicated, to equipment requirements height, need to
Totally, carry out in the preferable laboratory of seal.And, for making reactant react quickly and efficiently with substrate active part, join
Compound need to have preferable dissolubility in a solvent.Thus design invention one is orientable, self assembling process is simple and it is steady to be formed
Qualitative height, reproducible, film layer adjustable molecular film method is the most necessary.
Summary of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of Graphene-ruthenium complex multilamellar multiple
Close film and the method preparing Graphene-ruthenium complex multilayer complex films.In symmetry ruthenium complex molecule a pair in the present invention
Pyrenyl and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with there is cancellated π-electronic environment
Graphene interact, form orderly composite membrane, the Graphene that the present invention obtains-ruthenium complex multilayer complex films associating two
Kind of the respective advantage of material, compared with single Graphene or ruthenium complex self-assembled film more in a organized way, chemical property
Significantly improve.The present invention at room temperature uses simple receptacle the most operable, it is not necessary to specific condition and the instrument of complex and expensive, this
Bright it is achieved through the following technical solutions.
A kind of Graphene-ruthenium complex multilayer complex films, this multilayer complex films is the most folded by repeating on the composite membrane of substrate
Add symmetry ruthenium complex or Graphene and form multilayer complex films, in this substrate composite membrane in symmetry ruthenium complex molecule one
Pyrenyl and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with there is cancellated π-Electron Ring
The Graphene in border interacts, and the composite membrane of substrate up the first tunic is symmetry ruthenium complex, and the second layer is Graphene, the
Trilamellar membrane is symmetry ruthenium complex, so repeats, and wherein odd number is symmetry ruthenium complex layer, and even number is graphene layer, should
Symmetry ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Chemical general formula as follows:
。
Described Graphene-ruthenium complex multilayer complex films has excellent optical, electrical chemical property.
A kind of method preparing Graphene-ruthenium complex multilayer complex films, it specifically comprises the following steps that
Step 1, the preparation of ruthenium complex solution: prepare ruthenium complex to symmetry ruthenium complex addition dichloromethane molten
Liquid；
Step 2, the preparation of graphene dispersing solution: SDS is dissolved in the water and obtains the SDS aqueous solution that concentration is 2%, by stone
Ink alkene is that 2:10 ~ 4:10mg/ml ultrasound wave is dispersed in SDS aqueous solution according to the quality of Graphene and the volume ratio of SDS aqueous solution
In, after ultrasound wave dispersion processes, centrifugation removes bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/ml；
Step 3, the surface of HOPG process: are pressed against by adhesive tape on HOPG surface, then peel off, obtain new smooth conduction
Surface；
Self assembly ruthenium complex in step 4, HOPG substrate: the conductive surface submergence smooth for HOPG that will process through step 3
In the ruthenium complex solution that step 1 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping, with two
Chloromethanes cleans up rear noble gas and dries up, and i.e. obtains the HOPG electrode that ruthenium complex is modified；
Step 5, prepare Graphene-ruthenium complex composite membrane: the HOPG electrode modified through ruthenium complex step 4 obtained
Being immersed in the graphene dispersing solution that step 2 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping and uses
Methanol cleaning, noble gas dries up, and can prepare Graphene-ruthenium complex composite membrane；
Step 6, repetition step 4 and step 5, obtain the Graphene-ruthenium complex multilayer complex films of the different number of plies, Qi Zhongqi
Several layers is ruthenium complex, and even level is graphene layer.
In described step 1, the concentration of ruthenium complex solution is 50 μMs.
In described step 2, ultrasonic dispersing time is 0.5 ~ 1.5h, and the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
In described step 4, dip time is 6 ~ 12h.
In described step 5, dip time is 10 ~ 24h.
The invention has the beneficial effects as follows:
1, a pair pyrenyl in this symmetry ruthenium complex molecule and the effect by non-covalent bond of the HOPG surface, join ruthenium
Adduct molecule is fixed on HOPG surface, and pyrenyl and the Graphene with cancellated π-electronic environment are passed through π-π phase by another
Interaction, is fixed on Graphene in ruthenium complex monomolecular film, thus realize ruthenium complex/graphene composite film from group
Dress, and it is prevented from Graphene self reunion so that ruthenium complex molecule can be uniformly adhered to graphenic surface, has rule
The layer structure of rule, fully ensures that the uniform single degree of scatter of Graphene in material, and the ruthenium that can increase graphenic surface is joined
Adduct molecule adhesion amount.
2, the ruthenium complex [Ru (Py used in the present invention4G2MeBip2)](PF6)2Preferably dissolving is had in multi-solvents
Degree, beneficially coordination compound reacts quickly and efficiently with substrate active part, thus improves the efficiency of self assembly and self-assembled film
Quality.
3, the composite membrane that the present invention obtains is modified the most fully in conductive substrates, has good mechanically and chemically stablizing
Property, Graphene and ruthenium complex are compound can combine the respective advantage of bi-material, with single Graphene or ruthenium complex from
Component film is compared more in a organized way, chemical property significantly improves.HOPG electrode after modified is anode, has excellent
Optical, electrical chemical property, can be used for the fields such as DSSC.
4, the present invention at room temperature uses simple receptacle the most operable, it is not necessary to specific condition and the instrument of complex and expensive, with
Other laminated assembling technology is compared, and the present invention is whole, and to be self-assembled into membrane process technique easily controllable, simple to operate, preparation cost
Low, raw material is easy to get, it is not necessary to surface preparation, composite membrane and substrate bond strength are high, and film forming matter is not by substrate sizes and shape
Limiting, the thin film of preparation has good mechanically and chemically stability, the thickness of thin film and structure-controllable, and film forming repeatability
Good.
Accompanying drawing explanation
Fig. 1 is the structural representation of Graphene of the present invention-ruthenium complex multilayer complex films；
Fig. 2 is that the surface contact angle of Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 1 prepares is with group
The situation of change of the dress number of plies；
Fig. 3 is the cyclic voltammogram of Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 1 prepares；
Fig. 4 is that the surface contact angle of Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 2 prepares is with group
The situation of change of the dress number of plies；
Fig. 5 is the cyclic voltammogram of Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 2 prepares；
Fig. 6 is that the surface contact angle of Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 3 prepares is with group
The situation of change of the dress number of plies；
Fig. 7 is the cyclic voltammetric of self assembly Graphene-ruthenium complex multilayer complex films that the embodiment of the present invention 3 prepares
Figure.
In figure: 1-HOPG substrate, 2-ruthenium complex molecular film layer, 3-graphene layer.
Detailed description of the invention
Below in conjunction with the accompanying drawings and detailed description of the invention, the invention will be further described.
Embodiment 1
This Graphene-ruthenium complex multilayer complex films, as it is shown in figure 1, this multilayer complex films is by weight on the composite membrane of substrate
Multiple orderly superposition symmetry ruthenium complex or Graphene form 6 layers of composite membrane, and in this substrate composite membrane, symmetry ruthenium complex divides
A pair pyrenyl in son and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with have cancellated
The Graphene of π-electronic environment interacts, and the composite membrane of substrate up the first tunic is symmetry ruthenium complex, and the second layer is
Graphene, third layer film is symmetry ruthenium complex, and the 4th layer is Graphene, adds substrate composite membrane, 6 layers altogether, Qi Zhongqi
Number is symmetry ruthenium complex layer, and even number is graphene layer, this symmetry ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Change
Formula is as follows:
。
This prepares the method for Graphene-ruthenium complex multilayer complex films, and it specifically comprises the following steps that
Step 1, the preparation of ruthenium complex solution: add 20ml dichloromethane to 2.312mg symmetry ruthenium complex and prepare
Concentration is 50uM ruthenium complex solution；
Step 2, the preparation of graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) it is dissolved in 10ml water and obtains
Concentration is 2%(w/v) SDS aqueous solution, be 4 by 4mg Graphene according to the quality of Graphene and the volume ratio of SDS aqueous solution:
10mg/ml ultrasound wave is dispersed in SDS aqueous solution, and ultrasound wave dispersion moves in centrifuge, at 15krpm rotating speed after processing 0.5h
Lower centrifugation 1h, removes bottom residues, obtains the graphene dispersing solution that concentration is 0.3mg/ml；
Step 3, the surface of HOPG process: are pressed against by adhesive tape on HOPG surface, then peel off, obtain new smooth conduction
Surface；
Self assembly ruthenium complex in step 4, HOPG substrate: the conductive surface submergence smooth for HOPG that will process through step 3
In the ruthenium complex solution that step 1 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping 6h, uses
Dichloromethane cleans up rear noble gas and dries up, and i.e. obtains the HOPG electrode that ruthenium complex is modified；
Step 5, prepare Graphene-ruthenium complex composite membrane: step 5 is obtained the HOPG electrode leaching modified through ruthenium complex
Not in the graphene dispersing solution that step 2 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping 10h
With methanol cleaning, noble gas dries up, and can prepare Graphene-ruthenium complex composite membrane；
Step 6, repeat step 4 and step 5 twice, obtain the HOPG-Graphene-ruthenium complex composite membrane of 6 layers, wherein
Odd-level is ruthenium complex, and even level is graphene layer.
6 layers of composite film surface contact angle test of Graphene-ruthenium complex that the present embodiment prepares: the HOPG before modification
The contact angle on surface is 59.0 °, and the surface contact angle of the HOPG after assembling substrate ruthenium complex is 81.3 °, improves surface and dredges
Aqueous, this is because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, after continuing assembling substrate graphene layer, base
The contact angle on sheet surface is 61.4 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complex, substrate surface is graphite
Alkene, reduces the hydrophobicity of substrate surface, and after continuing assembling film layer, the contact angle on surface alternately becomes near substantially 81 ° and 61 °
Change, as shown in Figure 2.
The electrochemical property test of 6 layers of composite membrane of Graphene-ruthenium complex that the present embodiment prepares: after modified
HOPG substrate is anode, uses cyclic voltammetry to judge to be circulated the HOPG substrate after modifying the test of volt-ampere.Experiment institute
Being the AL660-C electrochemical analyser that BAS company of the U.S. produces with instrument, parameter is provided that initial potential is 0V；High potential
For 1.2V；Electronegative potential is 0V；Initial stage scanning is Poaitive；Scanning times is 6 times；Waiting time is 3～5s；Sensitivity selects
It is 10 μ A；Filtering parameter is 50Hz；Amplification 1；Scanning speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF during mensuration6Solution (solvent is anhydrous MeCN), as electrolyte, uses
Before be dried under vacuum 3h, the HOPG substrate after modification is as working electrode, Ag/AgNO3As reference electrode, Pt line is as right
Compare electrode.First being passed through 20 minutes nitrogen before experiment and remove the oxygen in solution, the data of mensuration carry out current potential correction.After being modified
Substrate voltammogram as shown in Figure 3.
The quantity of electric charge of HOPG substrate and amount of coating are calculated by formula (1) and (2) respectively.
(1)
Wherein, Q: the quantity of electric charge, C；
A: peak area, dots；
B: the area of chosen region B, dots；
IB: the electric current of B, A；
PB: the voltage of B, V；
V: scanning speed, V/s.
(2)
Wherein, Г: amount of coating, mol/cm2；
Q: the quantity of electric charge, C；
F:Faraday constant, 96485C/mol；
N: electron number；
A: contact area, 0.26cm2。
It is calculated the electric charge through the complex film modified HOPG electrode of 6 layer graphenes-ruthenium complex according to formula (1) and (2)
Amount is 5.749 × 10-6C, amount of coating is 1.146 × 10-10 mol/cm2。
Embodiment 2
This Graphene-ruthenium complex multilayer complex films, as it is shown in figure 1, this multilayer complex films is by weight on the composite membrane of substrate
Multiple orderly superposition symmetry ruthenium complex or Graphene form 8 layers of composite membrane, and in this substrate composite membrane, symmetry ruthenium complex divides
A pair pyrenyl in son and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with have cancellated
The Graphene of π-electronic environment interacts, and the composite membrane of substrate up the first tunic is symmetry ruthenium complex, and the second layer is
Graphene, third layer film is symmetry ruthenium complex, and the 4th layer is Graphene, and layer 5 film is symmetry ruthenium complex, the 6th
Layer is Graphene, adds substrate composite membrane, and 8 layers altogether, wherein odd number is symmetry ruthenium complex layer, and even number is graphene layer,
This symmetry ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Chemical general formula as follows:
。
This prepares the method for Graphene-ruthenium complex multilayer complex films, and it specifically comprises the following steps that
Step 1, the preparation of ruthenium complex solution: add 25ml dichloromethane to 2.890mg symmetry ruthenium complex and prepare
Concentration is 50uM ruthenium complex solution；
Step 2, the preparation of graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) it is dissolved in 10ml water and obtains
Concentration is 2%(w/v) SDS aqueous solution, by 3.5mg Graphene according to the quality of Graphene with the volume ratio of SDS aqueous solution be
3.5:10mg/ml ultrasound wave is dispersed in SDS aqueous solution, and ultrasound wave dispersion moves to, in centrifuge, turn at 15krpm after processing 1h
The lower centrifugation 2.5h of speed, removes bottom residues, obtains the graphene dispersing solution that concentration is 0.26mg/ml；
Step 3, the surface of HOPG process: are pressed against by adhesive tape on HOPG surface, then peel off, obtain new smooth conduction
Surface；
Self assembly ruthenium complex in step 4, HOPG substrate: the conductive surface submergence smooth for HOPG that will process through step 3
In the ruthenium complex solution that step 1 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping 8h, uses
Dichloromethane cleans up rear noble gas and dries up, and i.e. obtains the HOPG electrode that ruthenium complex is modified；
Step 5, prepare Graphene-ruthenium complex composite membrane: the HOPG electrode modified through ruthenium complex step 5 obtained
Being immersed in the graphene dispersing solution that step 2 obtains, slight concussion removes bubble, at room temperature takes out HOPG base after dipping 15h
Sheet methanol cleaning, noble gas dries up, and can prepare Graphene-ruthenium complex composite membrane；
Step 6, repeat step 4 and step 5 three times, obtain the Graphene-ruthenium complex composite membrane, wherein odd number of 8 layers
Layer is ruthenium complex, and even level is graphene layer.
8 layers of composite film surface contact angle test of Graphene-ruthenium complex that the present embodiment prepares: the HOPG before modification
The contact angle on surface is 59.4 °, and the surface contact angle of the HOPG after assembling substrate ruthenium complex is 81.0 °, improves surface and dredges
Aqueous, this is because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, after continuing assembling substrate graphene layer, base
The contact angle on sheet surface is 61.2 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complex, substrate surface is graphite
Alkene, reduces the hydrophobicity of substrate surface, and after continuing assembling film layer, the contact angle on surface alternately becomes near substantially 81 ° and 61 °
Change, as shown in Figure 4.
The electrochemical property test of 8 layers of composite membrane of Graphene-ruthenium complex that the present embodiment prepares: after modified
HOPG substrate is anode, uses cyclic voltammetry to judge to be circulated the HOPG substrate after modifying the test of volt-ampere.Experiment institute
Being the AL660-C electrochemical analyser that BAS company of the U.S. produces with instrument, parameter is provided that initial potential is 0V；High potential
For 1.2V；Electronegative potential is 0V；Initial stage scanning is Poaitive；Scanning times is 6 times；Waiting time is 3～5s；Sensitivity selects
It is 10 μ A；Filtering parameter is 50Hz；Amplification 1；Scanning speed (unit is V/s) is respectively set as according to experiment needs:
0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF during mensuration6Solution (solvent is anhydrous MeCN), as electrolyte, uses
Before be dried under vacuum 3h, the HOPG substrate after modification is as working electrode, Ag/AgNO3As reference electrode, Pt line is as right
Compare electrode.First being passed through 20 minutes nitrogen before experiment and remove the oxygen in solution, the data of mensuration carry out current potential correction.After being modified
Substrate voltammogram as shown in Figure 5.
It is calculated the electric charge through the complex film modified HOPG electrode of 8 layer graphenes-ruthenium complex according to formula (1) and (2)
Amount is 7.481 × 10-6C, amount of coating is 1.491 × 10-10mol/cm2。
Embodiment 3
This Graphene-ruthenium complex multilayer complex films, as it is shown in figure 1, this multilayer complex films is by weight on the composite membrane of substrate
Multiple orderly superposition symmetry ruthenium complex or Graphene form 10 layers of composite membrane, and in this substrate composite membrane, symmetry ruthenium complex divides
A pair pyrenyl in son and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with have cancellated
The Graphene of π-electronic environment interacts, and the composite membrane of substrate up the first tunic is symmetry ruthenium complex, and the second layer is
Graphene, third layer film is symmetry ruthenium complex, and the 4th layer is Graphene, and layer 5 film is symmetry ruthenium complex, the 6th
Layer is Graphene, and layer 7 film is symmetry ruthenium complex, and the 8th layer is Graphene, adds substrate composite membrane, 10 layers altogether, its
Middle odd number is symmetry ruthenium complex layer, and even number is graphene layer, this symmetry ruthenium complex [Ru (Py4G2MeBip2)](PF6)2
Chemical general formula as follows:
。
This prepares the method for Graphene-ruthenium complex composite membrane, and it specifically comprises the following steps that
Step 1, the preparation of ruthenium complex solution: add 30ml dichloromethane to 3.468 symmetry ruthenium complexes and prepare dense
Degree is 50uM ruthenium complex solution；
Step 2, the preparation of graphene dispersing solution: by 0.2gSDS(sodium lauryl sulphate) it is dissolved in 10ml water and obtains
Concentration is 2%(w/v) SDS aqueous solution, by 2.5mg Graphene according to the quality of Graphene with the volume ratio of SDS aqueous solution be
2.5:10mg/ml ultrasound wave is dispersed in SDS aqueous solution, and ultrasound wave dispersion moves in centrifuge, at 15krpm after processing 1.5h
Centrifugation 3h under rotating speed, removes bottom residues, obtains the graphene dispersing solution that concentration is 0.15mg/ml；
Step 3, the surface of HOPG process: are pressed against by adhesive tape on HOPG surface, then peel off, obtain new smooth conduction
Surface；
Self assembly ruthenium complex in step 4, HOPG substrate: the conductive surface submergence smooth for HOPG that will process through step 3
In the ruthenium complex solution that step 1 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping 12h, uses
Dichloromethane cleans up rear noble gas and dries up, and i.e. obtains the HOPG electrode that ruthenium complex is modified；
Step 5, Graphene-ruthenium complex composite membrane: the HOPG electrode submergence modified through ruthenium complex that step 5 is obtained
In the graphene dispersing solution that step 2 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping 24h and uses
Methanol cleaning, noble gas dries up, and can prepare Graphene-ruthenium complex composite membrane；
Step 6, repeat step 4 and step 5 four times, obtain the Graphene-ruthenium complex composite membrane, wherein odd number of 10 layers
Layer is ruthenium complex, and even level is graphene layer.
10 layers of composite film surface contact angle test of Graphene-ruthenium complex that the present embodiment prepares: before modification
The contact angle on HOPG surface is 59.3 °, and the surface contact angle of the HOPG after assembling substrate ruthenium complex is 81.3 °, improves table
Face hydrophobicity, this is because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, continues assembling substrate graphene layer
After, the contact angle of substrate surface is 61.6 °, this is because Graphene has been fixed on the hydrophobic group of ruthenium complex, and substrate surface
For Graphene, reducing the hydrophobicity of substrate surface, after continuing assembling film layer, the contact angle on surface is near substantially 81 ° and 61 °
Alternate, as shown in Figure 6.
The electrochemical property test of 10 layers of composite membrane of Graphene-ruthenium complex that the present embodiment prepares: after modified
HOPG substrate be anode, use cyclic voltammetry to judge the HOPG substrate after modifying and be circulated the test of volt-ampere.Experiment
Instrument is the AL660-C electrochemical analyser that BAS company of the U.S. produces, and parameter is provided that initial potential is 0V；High electricity
Position is 1.2V；Electronegative potential is 0V；Initial stage scanning is Poaitive；Scanning times is 6 times；Waiting time is 3～5s；Sensitivity is selected
It is selected as 10 μ A；Filtering parameter is 50Hz；Amplification 1；Scanning speed (unit is V/s) needs to set respectively according to experiment
For: 0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF during mensuration6Solution (solvent is anhydrous MeCN) as electrolyte,
Being dried under vacuum 3h before using, the HOPG substrate after modification is as working electrode, Ag/AgNO3As reference electrode, Pt line is made
For comparison electrode.First being passed through 20 minutes nitrogen before experiment and remove the oxygen in solution, the data of mensuration carry out current potential correction.Repaiied
The voltammogram of the substrate after decorations is as shown in Figure 7.
The quantity of electric charge of HOPG substrate and amount of coating are calculated by formula (1) and (2) respectively.
(1)
Wherein, Q: the quantity of electric charge, C；
A: peak area, dots；
B: the area of chosen region B, dots；
IB: the electric current of B, A；
PB: the voltage of B, V；
V: scanning speed, V/s.
(2)
Wherein, Г: amount of coating, mol/cm2；
Q: the quantity of electric charge, C；
F:Faraday constant, 96485C/mol；
N: electron number；
A: contact area, 0.26cm2。
It is calculated the electric charge through the complex film modified HOPG electrode of 10 layer graphenes-ruthenium complex according to formula (1) and (2)
Amount is 5.749 × 10-6C, amount of coating is 1.146 × 10-10 mol/cm2。
Above in conjunction with accompanying drawing, the detailed description of the invention of the present invention is explained in detail, but the present invention is not limited to above-mentioned
Embodiment, in the ken that those of ordinary skill in the art are possessed, it is also possible to before without departing from present inventive concept
Put that various changes can be made.
Claims (5)
1. the method preparing Graphene-ruthenium complex multilayer complex films, this multilayer complex films is by weight on the composite membrane of substrate
Multiple orderly superposition symmetry ruthenium complex or Graphene form multilayer complex films, and in this substrate composite membrane, symmetry ruthenium complex divides
A pair pyrenyl in son and HOPG are fixed on HOPG interface by non-covalent bond effect, another to pyrenyl with have cancellated
The Graphene of π-electronic environment interacts, and the composite membrane of substrate up the first tunic is symmetry ruthenium complex, and the second layer is
Graphene, third layer film is symmetry ruthenium complex, so repeats, and wherein odd number is symmetry ruthenium complex layer, and even number is stone
Ink alkene layer, this symmetry ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Chemical general formula as follows:
,
It is characterized in that specifically comprising the following steps that
Step 1, the preparation of ruthenium complex solution: add dichloromethane to symmetry ruthenium complex and prepare ruthenium complex solution；
Step 2, the preparation of graphene dispersing solution: SDS is dissolved in the water and obtains the SDS aqueous solution that concentration is 2%w/v, by graphite
Alkene is that 2:10 ~ 4:10mg/mL ultrasound wave is dispersed in SDS aqueous solution according to the quality of Graphene and the volume ratio of SDS aqueous solution,
After ultrasound wave dispersion processes, centrifugation removes bottom residues, obtains the graphene dispersing solution that concentration is 0.1 ~ 0.3mg/mL；
Step 3, the surface of HOPG process: are pressed against by adhesive tape on HOPG surface, then peel off, obtain new smooth conductivity meter
Face；
Self assembly ruthenium complex in step 4, HOPG substrate: conductive surface smooth for the HOPG processed through step 3 is immersed in step
In the ruthenium complex solution that rapid 1 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate after dipping, uses dichloromethane
Alkane cleans up rear noble gas and dries up, and i.e. obtains the HOPG electrode that ruthenium complex is modified；
Step 5, prepare Graphene-ruthenium complex composite membrane: the HOPG electrode submergence modified through ruthenium complex step 4 obtained
In the graphene dispersing solution that step 2 obtains, slight concussion removes bubble, at room temperature takes out HOPG substrate methanol after dipping
Cleaning, noble gas dries up, and can prepare Graphene-ruthenium complex composite membrane；
Step 6, repeat step 4 and step 5, obtain the Graphene of the different number of plies-ruthenium complex multilayer complex films, wherein odd-level
For ruthenium complex, even level is graphene layer.
The method preparing Graphene-ruthenium complex multilayer complex films the most according to claim 1, it is characterised in that: described
In step 1, the concentration of ruthenium complex solution is 50 μMs.
The method preparing Graphene-ruthenium complex multilayer complex films the most according to claim 1, it is characterised in that: described
In step 2, ultrasonic dispersing time is 0.5 ~ 1.5h, and the centrifugation time is 1 ~ 3h, and rotating speed is 15krpm.
The method preparing Graphene-ruthenium complex multilayer complex films the most according to claim 1, it is characterised in that: described
In step 4, dip time is 6 ~ 12h.
The method preparing Graphene-ruthenium complex multilayer complex films the most according to claim 1, it is characterised in that: described
In step 5, dip time is 10 ~ 24h.
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