CN104576071B - A kind of ruthenium complex monomolecular film and the method that ruthenium complex monomolecular film is prepared on HOPG - Google Patents
A kind of ruthenium complex monomolecular film and the method that ruthenium complex monomolecular film is prepared on HOPG Download PDFInfo
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Abstract
A kind of method that ruthenium complex monomolecular film is prepared the present invention relates to ruthenium complex monomolecular film and on HOPG, belongs to molecular self-assembling technical field of chemistry.Pyrenyl in the ruthenium complex monomolecular film in ruthenium complex is interacted with the HOPG with pi-electron environment by π π, and two pyrenyls of ruthenium complex molecule are fixed on into HOPG interfaces, and the ruthenium complex formula is [Ru (Py4G2MeBip2)](PF6)2.Ruthenium complex solution is prepared first, then HOPG progress is surface-treated, and ruthenium complex self assembly is finally prepared into ruthenium complex monomolecular film in HOPG substrates using with spin-coating method or infusion process.The present invention prepares ruthenium complex monomolecular film using two methods, and the ruthenium complex monomolecular film of preparation has good mechanically and chemically stability, many advantages, such as thickness of molecular film is controllable.
Description
Technical field
A kind of method that ruthenium complex monomolecular film is prepared the present invention relates to ruthenium complex monomolecular film and on HOPG, category
In molecular self-assembling technical field of chemistry.
Background technology
The preparation for developing into molecular device and application of numerator self-assembly technique bring new hope.Unimolecular layer membrane is to dividing
The research of sub- device provides many opportunities challenging on Science and Technology.Unimolecular layer membrane self-assembling technique is logical
Cross the molecule in solution to be diffused on the substrate of immersion in the solution, them is occurred physical absorption or chemical action, be formed with
The molecular assembled system of sequence.Unimolecular layer membrane self assembly is that high-sequential and tool are directive, and can be with many groups
Interaction, so the diversified surface with Specific Interactions can be obtained by accurate Chemical Control.
Ruthenium complex is because its dissolubility is good, stability is good, oxidation-reduction potential than relatively low, high electrochemical luminescence efficiency and
Good compatibility and possess excellent electrochemical luminescence performance.The preferable dissolubility of ruthenium complex determines that it can be by changing
Different anion makes it have good dissolubility in water and organic solvent.Its oxidation-reduction potential than relatively low, therefore
It is easy to carry out electron-transfer reaction under the voltage that can be obtained, easily produces excitation state, produces luminescence phenomenon.In addition, ruthenium
(II) complex is in dye sensitization TiO2Also very high photoelectric transformation efficiency is shown on nano-electrode.
Ruthenium outermost layer has 4d75s1Structure, the common valence state of its ion is Ru (I), Ru (II) and Ru (III), and is easy to shape
Into the complex of hexa-coordinate.Ruthenium complex is due to thermodynamic stability is good, photochemical light physical message is abundant, excitation state is anti-
Should activity is high and long lifespan and the characteristic such as luminescent properties are good, be widely used in chemiluminescence, electro transfer, non-thread at present
Property optical material, molecular light switch, molecular recognition, the research in the field such as sensor.
HOPG(Highly Oriented Pyrolytic Graphite, highly oriented pyrolytic graphite)It is a kind of new high-purity
Carbon is spent, is a kind of pyrolytic graphite obtained New graphite material after high temperature high pressure process, HOPG most prominent functions are that have one
The surface of individual unusual light and electrical conductance, its surface are almost a graphite linings, the atom of the highly directional orthohexagonal of standard
Order is arranged 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 HOPG surface, is then torn, and a thin layer of HOPG will be stained with adhesive tape, and it is new newly to split top layer
Smooth conductive surface, may be used as sample base material., can be mutual by π-π because HOPG has π-electronic environment
Effect, which connects other, to be had the complex of π-electronic environment to prepare the molecular film for possessing excellent properties.
The research to the method for the sufficient ruthenium complex monomolecular film of self assembly two on HOPG domestic at present has not been reported.It is public
The self-assembling method for the molecular film opened mainly has:
" a kind of preparation side of self assembly covalent cross-linking NF membrane disclosed in Publication No. CN103223302A Chinese patent
In method ", a kind of preparation method of self assembly covalent cross-linking NF membrane is disclosed, basement membrane is pre-processed, its surface is taken energy
It is immersed in after occurring the functional group of electrostatic interaction with polyelectrolyte in function polyelectrolyte solution, takes out basement membrane and rinse behind surface and soak
Steep in the polyelectrolyte solution of opposite charges is carried therewith, finally take the film out the crosslinking agent that twain-aldehyde compound is immersed in after rinsing
In, obtain the self assembly covalent cross-linking NF membrane with biocidal property.
" a kind of electro-deposition system of photo-crosslinking type bio-based coating disclosed in Publication No. CN103757683A Chinese patent
In Preparation Method ", the invention provides a kind of electro-deposition preparation method of photo-crosslinking type bio-based coating.The preparation method, which is utilized, to be contained
The amphiphilic ionic bio-based Macromolecular self-assembly of photosensitive group obtains micella particle, by constant potential electro-deposition techniques in doctor
Metal surface film forming is used, micella particle is crosslinked through ultraviolet lighting cross-linking reaction, the doctor based on self-assembled micelle film is obtained
Use biological coating material.
" processed disclosed in Publication No. CN103121659A Chinese patent with photoetching process on highly oriented pyrolytic graphite
In the method for micro-structural ", HOPG surfaces are ground first by grinder, it is polished and carries out making HOPG's after surface clean
Mask, spin coating photoresist is used as SiO2The mask of film or metallic film, carries out photoetching, graphical HOPG and covers successively afterwards
Film, etching HOPG, removing photoresist, removing HOPG mask obtain the micro-structural on highly oriented pyrolytic graphite.
" patterning BiFeO disclosed in Publication No. CN102163486A Chinese patent3It is prepared by the photoetching self assembly of film
In method ", BiFeO is patterned the invention discloses one kind3The photoetching self-assembly preparation method thereof of film, this method will be through ultraviolet light
Glass substrate after irradiation, which is placed in OTS- toluene solutions, soaks, and makes substrate surface one layer of OTS monomolecular film of formation, Zhi Hou
Under the covering of photomask, irradiate under ultraviolet light, the function self-assembled film patterned is finally placed in preparation BiFeO3
In precursor solution, deposition, ultrasonic oscillation cleaning, annealing obtains the patterning BiFeO of photoetching self assembly3Film.
There is provided include inorganic knot in " method of coating base material " disclosed in Publication No. CN102036757A Chinese patent
The coating compound of structure and liquid-carrier, at least a portion of base material is immersed under liquid side in phase, by the base material and liquid
Dignity is lower to be separated, so that at least a portion of coating is transferred on base material, then at least the one of the base material of the coating
Part is heated, and the base material coated, the base material used in this method need to be inorganic substrate, the inorganic structure at least one of heating
Partially sinter, after heating, the angle between adjacent inorganic structure is more than 90 degree.
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 high, the reproducible molecule film method of stability
It 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 ruthenium complex monomolecular film and
The method that ruthenium complex monomolecular film is prepared on HOPG.Pyrenyl in the present invention in ruthenium complex molecule is with having π-electronic environment
HOPG by interaction, two pyrenyls of ruthenium complex molecule are fixed on HOPG interfaces, so as to realize in HOPG substrates
Upper self assembly ruthenium complex monomolecular film.Simultaneously OPG- ruthenium complex monomolecular films are prepared using two methods:One kind is rotation Tu
Method, another is infusion process.Built-up time has been greatly saved using spin-coating method and infusion process assembling ruthenium complex monolayer, should
Method is simple to operate, and assembled layers modify uniform abundant in HOPG conductive substrates, be using simple receptacle at room temperature it is operable,
Without specific condition and equipment, the HOPG conductive substrates after modification have excellent electro-chemical activity, the ruthenium complex of preparation
Monomolecular film has good mechanically and chemically stability, and many advantages, such as thickness of molecular film is controllable is of the invention by following
Technical scheme is realized.
A kind of pyrenyl in ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-electronics
The HOPG of environment is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex
[Ru(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
The ruthenium complex monomolecular film has excellent light, Electricity Functional.
A kind of method that utilization spin-coating method prepares ruthenium complex monomolecular film on HOPG, it is comprised the following steps that:
Step 1, first by ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in tetrahydrofuran solution, is made
50uM ruthenium complex solution;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
Step 3, will be surface-treated through step 2 after HOPG substrates be fixed on rotation Tu instrument on, HOPG substrate surfaces be added dropwise
The ruthenium complex solution that step 1 is prepared, starts spin coating instrument, ruthenium complex is uniformly sprawled film forming, room temperature, which is placed, makes it certainly
So dry, remove HOPG substrates, inert gas is dried up after being cleaned with tetrahydrofuran, can prepare ruthenium complex unimolecule
Film, the HOPG modified through ruthenium complex monomolecular film is used as anode.
The spin coating instrument low rate start stage speed of rotation is 150 ~ 200rpm in the step 3, and the time is 3 ~ 5s, is rotated at a high speed
Speed is 700 ~ 1000rpm, and the time is 70 ~ 120s.
A kind of method that utilization infusion process prepares ruthenium complex monomolecular film on HOPG, it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:By ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane
In alkane solution, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
NW-TFT in step 3, HOPG substrates:The HOPG being surface-treated through step 2 is immersed in what step 1 configuration was obtained
In ruthenium complex solution, slight concussion removes bubble, takes out HOPG substrates after impregnating at room temperature, is cleaned up with dichloromethane
Inert gas is dried up afterwards, can prepare ruthenium complex monomolecular film, and the HOPG modified through ruthenium complex monomolecular film makees
For anode.
Dip time is 10 ~ 24h in the step 3.
Above-mentioned uM represents umol/L.
The beneficial effects of the invention are as follows:
1st, the pyrenyl in the ruthenium complex molecule is interacted with the HOPG with π-electronic environment by π-π, and ruthenium is matched somebody with somebody
Two pyrenyls of adduct molecule are fixed on HOPG interfaces, so that the self assembly ruthenium complex monomolecular film in HOPG substrates is realized,
Molecular film is firmly combined with HOPG substrates.
2nd, the ruthenium complex [Ru (Py used in the present invention4G2MeBip2)](PF6)2There is preferable dissolving in multi-solvents
Degree, is conducive to the complex quickly and efficiently to be reacted with substrate active part, so as to improve the efficiency and self-assembled film of self assembly
Quality.
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 HOPG, being formed has light, the self assembly molecule film of Electricity Functional, and Iy self-assembled layer divides in substrate
Cloth is uniform, and with good electro-chemical activity and photophysical property.HOPG electrodes after modification are anode, with 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.
5th, graphene is assembled into monomolecular film by the present invention using spin-coating method, only needs 70 ~ 120s, more other technique phases
Than, the operating time is greatly shortened, packaging efficiency is improved, and the film prepared has feature photoelectric property.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 prepares ruthenium complex monomolecular film voltammogram using spin-coating method;
Fig. 2 is that the embodiment of the present invention 1 prepares ruthenium complex monomolecular film sweep speed and electric current pass using spin-coating method
System's figure;
Fig. 3 is the voltammogram that the embodiment of the present invention 2 prepares ruthenium complex monomolecular film using spin-coating method;
Fig. 4 is the sweep speed and electric current that the embodiment of the present invention 2 prepares ruthenium complex monomolecular film using spin-coating method
Graph of a relation;
Fig. 5 is the voltammogram that the embodiment of the present invention 3 prepares ruthenium complex monomolecular film using spin-coating method;
Fig. 6 is the sweep speed and electric current that the embodiment of the present invention 3 prepares ruthenium complex monomolecular film using spin-coating method
Graph of a relation.
Fig. 7 is the voltammogram that the embodiment of the present invention 4 prepares ruthenium complex monomolecular film using infusion process;
Fig. 8 is the scanning for the HOPG substrates that the embodiment of the present invention 4 prepares ruthenium complex monomolecular film using infusion process
Speed and current relationship figure;
Fig. 9 is the voltammogram that the embodiment of the present invention 5 prepares ruthenium complex monomolecular film using infusion process;
Figure 10 is the sweep speed and electricity that the embodiment of the present invention 5 prepares ruthenium complex monomolecular film using infusion process
Flow relation figure;
Figure 11 is the voltammogram that the embodiment of the present invention 6 prepares ruthenium complex monomolecular film using infusion process;
Figure 12 is the sweep speed and electric current that the embodiment of the present invention 6 prepares ruthenium complex monomolecular film using infusion process
Graph of a relation.
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 HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using spin-coating method on HOPG, and it is comprised the following steps that:
Step 1, first by 2.312mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in 20ml tetrahydrofurans molten
In liquid, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
Step 3, will be surface-treated through step 2 after HOPG substrates be fixed on rotation Tu instrument on, HOPG substrate surfaces be added dropwise
The ruthenium complex solution that step 1 is prepared, starts spin coating instrument, and the low rate start stage speed of rotation is 150rpm, and the time is 5s,
High speed rotation rate is 700rpm, and the time is 120s, ruthenium complex is uniformly sprawled film forming, room temperature, which is placed, spontaneously dries it,
HOPG substrates are removed, inert gas is dried up after being cleaned with tetrahydrofuran, can prepare ruthenium complex monomolecular film, this is through ruthenium
The HOPG electrodes of complex monomolecular film modification are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 59.8 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 81.0 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep speed (unit is V/s) needs to set respectively according to experiment
It is set to:0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in continuous mode6Solution(Solvent is anhydrous MeCN)It is used as electrolysis
3h is dried under vacuum before matter, use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3It is used as reference electrode, Pt
Line 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 correction.
The voltammogram of substrate after to modification 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=5.795×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-6.672×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates 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 and obtain the quantities of electric charge of the HOPG electrodes through being modified through ruthenium complex monomolecular film and be
1.988×10-6C, amount of coating is 3.692 × 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 HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using spin-coating method on HOPG, and it is comprised the following steps that:
Step 1, first by 1.739mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in 15ml tetrahydrofurans molten
In liquid, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
Step 3, will be surface-treated through step 2 after HOPG substrates be fixed on rotation Tu instrument on, HOPG substrate surfaces be added dropwise
The ruthenium complex solution that step 1 is prepared, starts spin coating instrument, and the low rate start stage speed of rotation is 170rpm, and the time is 4s,
High speed rotation rate is 850rpm, and the time is 100s, ruthenium complex is uniformly sprawled film forming, room temperature, which is placed, spontaneously dries it,
HOPG substrates are removed, inert gas is dried up after being cleaned with tetrahydrofuran, can prepare ruthenium complex monomolecular film, this is through ruthenium
The HOPG electrodes of complex monomolecular film modification are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 59.7 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 81.2 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep 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 in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte,
3h is dried under vacuum before use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3As reference electrode, Pt lines are made
For 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.Repaiied
The voltammogram of substrate after decorations 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=4.514×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-5.046×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)The quantity of electric charge for calculating the HOPG electrodes for obtaining modifying through ruthenium complex monomolecular film is 1.867
×10-6 C, amount of coating is 3.721 × 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 HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using spin-coating method on HOPG, and it is comprised the following steps that:
Step 1, first by 2.89mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in 25ml tetrahydrofuran solutions
In, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
Step 3, will be surface-treated through step 2 after HOPG substrates be fixed on rotation Tu instrument on, HOPG substrate surfaces be added dropwise
The ruthenium complex solution that step 1 is prepared, starts spin coating instrument, and the low rate start stage speed of rotation is 200rpm, and the time is 3s,
High speed rotation rate is 1000rpm, and the time is 70s, ruthenium complex is uniformly sprawled film forming, room temperature, which is placed, spontaneously dries it,
HOPG substrates are removed, inert gas is dried up after being cleaned with tetrahydrofuran, can prepare ruthenium complex monomolecular film, this is through ruthenium
The HOPG electrodes of complex monomolecular film modification are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 61.0 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 81.9 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep 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 in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte,
3h is dried under vacuum before use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3As reference electrode, Pt lines are made
For 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.Repaiied
The voltammogram of substrate after decorations 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=5.401×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-6.317×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)Calculate obtain the modification of ruthenium complex monomolecular film HOPG electrode charge amounts be 1.879 ×
10-6 C, amount of coating is 3.745 × 10-11 mol/cm2。
Embodiment 4
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring
The HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using infusion process on HOPG, and it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:By 2.89mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in
In 25ml dichloromethane solutions, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
NW-TFT in step 3, HOPG substrates:The HOPG being surface-treated through step 2 is immersed in what step 1 configuration was obtained
In ruthenium complex solution, slight concussion removes bubble, impregnates HOPG substrates are taken out after 10h at room temperature, cleaned with dichloromethane
Inert gas drying, can prepare ruthenium complex monomolecular film after clean, and this is modified through ruthenium complex monomolecular film
HOPG electrodes are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 59.3 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 81.0 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep 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 in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte,
3h is dried under vacuum before use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3As reference electrode, Pt lines are made
For 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.Repaiied
The voltammogram of substrate after decorations is as shown in Figure 7.
Current value increases with the increase of sweep speed as can be seen from Figure 8, anode current ipaWith the letter of scan velocity V
Number relation is ipa=3.319×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-5.695×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)The quantity of electric charge for calculating the HOPG electrodes for obtaining modifying through ruthenium complex monomolecular film is 1.743
×10-6C, amount of coating is 3.474 × 10-11 mol/cm2。
Embodiment 5
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring
The HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using infusion process on HOPG, and it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:By 2.312mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in
In 20ml dichloromethane solutions, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
NW-TFT in step 3, HOPG substrates:The HOPG being surface-treated through step 2 is immersed in what step 1 configuration was obtained
In ruthenium complex solution, slight concussion removes bubble, impregnates HOPG substrates are taken out after 15h at room temperature, cleaned with dichloromethane
Inert gas drying, can prepare ruthenium complex monomolecular film after clean, and this is modified through ruthenium complex monomolecular film
HOPG electrodes are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 59.3 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 82.8 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep 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 in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte,
3h is dried under vacuum before use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3As reference electrode, Pt lines are made
For 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.Repaiied
The voltammogram of substrate after decorations is as shown in Figure 9.
Current value increases with the increase of sweep speed as can be seen from Figure 10, anode current ipaWith the letter of scan velocity V
Number relation is ipa=3.319×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-5.695×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)Calculating the quantity of electric charge obtained in the HOPG substrates after being modified through ruthenium complex monomolecular film is
1.813×10-6, amount of coating is 3.613 × 10-11 mol/cm2。
Embodiment 6
Pyrenyl in the ruthenium complex monomolecular film, the ruthenium complex monomolecular film in ruthenium complex is with having π-Electron Ring
The HOPG in border is interacted by π-π, two pyrenyls of ruthenium complex molecule is fixed on into HOPG interfaces, the ruthenium complex [Ru
(Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
。
This prepares the method for ruthenium complex monomolecular film using infusion process on HOPG, and it is comprised the following steps that:
The preparation of step 1, ruthenium complex solution:By 4.046mg ruthenium complexes [Ru (Py4G2MeBip2)](PF6)2It is dissolved in
In 30ml dichloromethane solutions, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conduction is obtained
Surface;
NW-TFT in step 3, HOPG substrates:The HOPG being surface-treated through step 2 is immersed in what step 1 configuration was obtained
In ruthenium complex solution, slight concussion removes bubble, impregnates HOPG substrates are taken out after 24h at room temperature, cleaned with dichloromethane
Inert gas drying, can prepare ruthenium complex monomolecular film after clean, and this is modified through ruthenium complex monomolecular film
HOPG electrodes are used as anode.
The surface contact angle test for the ruthenium complex monomolecular film that the present embodiment is prepared:HOPG tables after surface treatment
The contact angle in face is 61.3 °, and the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 81.5 °, surface parent
Aqueous reduction, because electrode surface is the hydrophobic group in exposed ruthenium complex molecule, meanwhile, the change of contact angle is also demonstrate,proved
Understand ruthenium complex monomolecular film on the NW-TFT that succeeded on HOPG.
The electrochemical property test for the ruthenium complex monomolecular film that the present embodiment is prepared:Through ruthenium complex monomolecular film
The HOPG electrodes of modification are anode, judge to carry out ruthenium complex monomolecular film the test of cyclic voltammetric using cyclic voltammetry.
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;It is sensitive
Degree selection is 10 μ A;Filtering parameter is 50Hz;Multiplication factor 1;Sweep 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 in continuous mode6Solution(Solvent is anhydrous MeCN)As electrolyte,
3h is dried under vacuum before use, the HOPG substrates after modification are used as working electrode, Ag/AgNO3As reference electrode, Pt lines are made
For 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.Repaiied
The voltammogram of substrate after decorations is as shown in figure 11.
Current value increases with the increase of sweep speed as can be seen from Figure 12, anode current ipaWith the letter of scan velocity V
Number relation is ipa=4.267×10-6V, cathode current ipbFunctional relation with scan velocity V is ipb=-5.071×10-6V, nothing
By being that anode current or cathode current are satisfied by ip ∝ V relations, it was demonstrated that ruthenium complex molecule is successfully assembled into HOPG substrates
On.The quantity of electric charge and amount of coating of HOPG substrates press formula respectively(1)With(2)Calculated.
According to formula(1)With(2)Calculating the quantity of electric charge obtained in the HOPG substrates after being modified through ruthenium complex monomolecular film is
1.761×10-6C, amount of coating is 3.509 × 10-11mol/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 (4)
1. ruthenium in a kind of method that utilization spin-coating method prepares ruthenium complex monomolecular film on HOPG, the ruthenium complex monomolecular film
Pyrenyl in complex is interacted with the HOPG with π-electronic environment by π-π, by two pyrenyls of ruthenium complex molecule
HOPG interfaces are fixed on, the ruthenium complex [Ru (Py4G2MeBip2)](PF6)2Chemical general formula it is as follows:
,
It is characterized in that comprising the following steps that:
Step 1, first by ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in tetrahydrofuran solution, is made 50uM's
Ruthenium complex solution;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conductivity meter is obtained
Face;
Step 3, will be surface-treated through step 2 after HOPG substrates be fixed on rotation Tu instrument on, HOPG substrate surfaces be added dropwise step 1
The ruthenium complex solution prepared, starts spin coating instrument, ruthenium complex is uniformly sprawled film forming, room temperature, which is placed, makes it do naturally
It is dry, HOPG substrates are removed, inert gas is dried up after being cleaned with tetrahydrofuran, can prepare ruthenium complex monomolecular film, should
The HOPG modified through ruthenium complex monomolecular film is used as anode.
2. the method that utilization spin-coating method according to claim 1 prepares ruthenium complex monomolecular film on HOPG, its feature
It is:The spin coating instrument low rate start stage speed of rotation is 150 ~ 200rpm in the step 3, and the time is 3 ~ 5s, and speed is rotated at a high speed
Rate is 700 ~ 1000rpm, and the time is 70 ~ 120s.
3. a kind of method that utilization infusion process prepares ruthenium complex monomolecular film on HOPG, in the ruthenium complex monomolecular film
Pyrenyl in ruthenium complex is interacted with the HOPG with π-electronic environment by π-π, by two pyrenes of ruthenium complex molecule
Base is fixed on HOPG interfaces, 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:By ruthenium complex [Ru (Py4G2MeBip2)](PF6)2It is dissolved in dichloromethane molten
In liquid, 50uM ruthenium complex solution is made;
The surface treatment of step 2, HOPG:Adhesive tape is pressed against on HOPG surfaces, then peeled off, new smooth conductivity meter is obtained
Face;
NW-TFT in step 3, HOPG substrates:The HOPG being surface-treated through step 2 is immersed in into the obtained ruthenium of step 1 configuration to match somebody with somebody
In polymer solution, slight concussion removes bubble, takes out HOPG substrates after impregnating at room temperature, is cleaned up with dichloromethane rear lazy
Property gas drying, ruthenium complex monomolecular film can be prepared, this through ruthenium complex monomolecular film modify HOPG be used as sun
Pole.
4. the method that utilization infusion process according to claim 3 prepares ruthenium complex monomolecular film on HOPG, its feature
It is:Dip time is 10 ~ 24h in the step 3.
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""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 * |
"pH-Dependent Electrochemical Behaviors of Ruthenium Complex/Carbon Nanotube Composites on Platinum and Pencil-lead Electrodes";Hiroaki Ozawa等;《Chemistry Letters》;20130905;第42卷(第9期);第1059-1061页 * |
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