CN104446645B - HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof - Google Patents
HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof Download PDFInfo
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Abstract
The invention discloses HOPG substrate of a kind of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof, it is fixed on HOPG conductive substrate by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule and obtains, method of the present invention is simple to operate, assembled layers is modified evenly fully in HOPG substrate, simple receptacle is at room temperature used to operate, without the need to specific condition and equipment, HOPG substrate after directed modification has excellent electro-chemical activity, the film of preparation has good machinery and chemical stability, the plurality of advantages such as the thickness of film is controlled.
Description
Technical field
The present invention relates to a kind of HOPG substrate and self-assembling method thereof of amphipathic ruthenium complex monomolecular film directed modification, be specifically related to a kind of in HOPG conductive substrates the amphipathic ruthenium complex of directed self assembly form monomolecular film and the obtained method through the HOPG substrate of directed modification, belong to molecular self-assembling chemical field.
Background technology
The preparations and applicatio of self-assembled film is the focus of current self assembly area research.By molecular self-assembling, we can obtain the self-assembled material with the functions such as excellence is optical, electrical, catalysis and characteristic, the self-assembled film material particularly obtaining now extensive concern all has wide practical use in device for non-linear optical, chemical biosensor, information storage material and organism promote coagulate tube, is subject to researcher and payes attention to widely and study.
The valence electron structure of ruthenium is 4d
75s
1structure, common ionic valence condition is Ru (I), Ru (II) and Ru (III).Due to the structure that it is special, ruthenium is easy to the complex that binding partner forms the octahedral structure of hexa-coordinate.Ruthenium complex has good redox active, and its activated centre generally includes the oxidation of central ion and the reduction of part.Ruthenium complex self-assembly method is the self assembly effect according to molecule, sets up at the molecular layer that electrode surface height of formation is orderly.
HOPG(HighlyOrientedPyrolyticGraphite, highly oriented pyrolytic graphite) be a kind of novel high purity Carbon Materials, be a kind of novel charcoal material that pyrolytic graphite obtains after high temperature high pressure process, its performance is close to single crystal graphite.HOPG is special Inorganic Non-metallic Materials, has performance and other series of characteristics of metal and plastics concurrently, obtains extensive use at industrial departments such as metallurgy, chemical industry, electric power and electronics, machinery, weaving and atomic energy.The most outstanding function of HOPG is the surface and the electrical conductance that have a unusual light.HOPG has layer structure, makes sample preparation very simple.Only with a double faced adhesive tape by being pressed on HOPG, then need peeling off, just can obtain new smooth conductive surface.Ruthenium complex at room temperature can be adsorbed to the self-assembled monolayer that formation on HOPG neatly aligns from solution, promotes the photoelectric properties of HOPG.
The research of the domestic method to the amphipathic ruthenium complex monomolecular film of self assembly directed on HOPG at present have not been reported.The self-assembling method of disclosed molecular film mainly contains:
Publication number is the Chinese patent disclosed " a kind of brass surfaces self-assembled film with corrosion inhibition and preparation method thereof " of CN102268715A, have employed anodizing technology, by the brass after surface preparation after NaCl aqueous solution Anodic Oxidation, in the ethanolic solution of lauryl mercaptan, carry out self assembly, obtain the self-assembled film that a kind of brass surfaces has corrosion inhibition.
Publication number is in the Chinese patent disclosed " having micropore self-assembled material of the double-deck wall of fluorescence identifying effect and preparation method thereof " of CN102838626A, with the supporting wall that the two carboxylic acids of rigidity and rigidity nitrogen heterocycles organic ligand are poromerics, metal centered by the metal ion with polygamy potential field geometric configuration, by the method for solvent heat self-assembled growth, prepare the micropore self-assembled material with double-deck organic wall.The prepared micropore self-assembled material duct size with double-deck organic wall is 5 ~ 20, is three-dimensional intercommunication duct and has characteristic fluorescence.
Publication number is in the Chinese patent disclosed " a kind of manufacture method of high-selectivity semiconductor film " of CN102376890A, titanium cyanogen nickel is adopted to be sensitive membrane material, nitrogen-nitrogen dimethyl formamide is self assembly solvent, on the propagation path of SAW (Surface Acoustic Wave) resonator surface or surface wave delay line, adopt self-assembling method titanium deposition cyanogen nickel film.The sensitive membrane of self assembly by after heat treatment to NO
2there is strong sensitiveness and high selectivity.
At present, the monomolecular film self-assembly method of complex is a kind of effective ways being conducive to control group assembling structure and form, can spontaneous height of formation is orderly by covalent bond or non-covalent bond on the surface of electrode monolayer.Self-assembled film molecules align is tight in order, but assembling process is complicated, high to equipment requirement.Thus a kind of orientable, self assembling process of design invention is simple and can form that stability is high, the molecular film method of favorable repeatability is very necessary.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides the HOPG substrate that a kind of amphipathic ruthenium complex monomolecular film is modified, pyrenyl in amphipathic ruthenium complex molecule is fixed in HOPG conductive substrates by the effect of non-covalent bond, form the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification, wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
。
Another object of the present invention is to provide a kind of self-assembling method of HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification, and concrete steps are as follows:
(1) preparation of amphipathic ruthenium complex solution: add ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 10 ~ 12, taking amphipathic ruthenium complex is dissolved in above-mentioned solution, and after regulating pH to 5 ~ 7 with HCl, obtained concentration is 49 ~ 51 μMs of amphipathic ruthenium complex solution;
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains new smooth conductive surface;
(3) NW-TFT of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG substrate after surface treatment is immersed in amphipathic ruthenium complex solution, slight concussion removing bubble, after at room temperature flooding 6 ~ 12h, taking-up ultra-pure water cleans up rear inert gas and dries up, and namely obtains the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification; The anode that HOPG substrate after this modification can be used as battery uses.
Described amphipathic ruthenium complex obtains with reference to method in patent application 201410450980.5 " a kind of dye-sensitized solar cells amphipathic benzimidazole ruthenium complex and preparation method thereof ".
Method of the present invention is simple to operate, assembled layers is modified evenly fully in HOPG substrate, simple receptacle is at room temperature used to operate, without the need to specific condition and equipment, HOPG substrate after directed modification has excellent electro-chemical activity, the plurality of advantages such as the film of preparation has good machinery and chemical stability, and the thickness of film is controlled.
The invention has the beneficial effects as follows:
1, the pyrenyl in this amphipathic ruthenium complex molecule and the surperficial effect by non-covalent bond of HOPG, the pyrenyl section of ruthenium complex molecule is fixed on HOPG interface, phosphate is exposed at electrode surface, thus realizing directed self assembly ruthenium complex monomolecular film in HOPG substrate, the surface of substrate is that hydrophily can continue to assemble other molecular films.
2, preparation method of the present invention obtains complex assembled layers firm on electrode, and directed Iy self-assembled layer is evenly distributed in substrate, and has good electro-chemical activity and photophysical property.HOPG electrode after modified is anode, has excellent optical, electrical chemical property, can be used for the fields such as battery.
3, the present invention at room temperature uses simple receptacle to operate, without the need to instrument and equipment and the specific condition of complexity, the whole membrane process technique that is self-assembled into is easy to control, simple to operate, preparation cost is low, and raw material is easy to get, film forming matter is not subject to the restriction of substrate sizes and shape, the film of preparation has good machinery and chemical stability, the thickness of film and structure-controllable, and film forming is reproducible.
Accompanying drawing explanation
Fig. 1 is the voltammogram of the not modified HOPG substrate of the present invention;
Fig. 2 is the voltammogram of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 1 prepares;
Fig. 3 is sweep speed and the current relationship figure of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 1 prepares;
Fig. 4 is the voltammogram of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 2 prepares;
Fig. 5 is sweep speed and the current relationship figure of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 2 prepares;
Fig. 6 is the voltammogram of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 3 prepares;
Fig. 7 is sweep speed and the current relationship figure of the HOPG substrate after amphipathic ruthenium complex monomolecular film directed modification that the embodiment of the present invention 3 prepares.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1: the HOPG substrate of this amphipathic ruthenium complex monomolecular film directed modification is fixed in HOPG conductive substrates by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complex monomolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 15ml ultra-pure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complex of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultra-pure water and be settled to 30ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains the surface of new smooth conduction;
(3) the directed self assembly of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultra-pure water after 6h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
By testing the surface contact angle of the HOPG conductive substrates under different preparing processes, result is as follows: the contact angle on the HOPG surface after surface treatment is 60.3 °, the surface contact angle of the HOPG after the amphipathic ruthenium complex monomolecular film of NW-TFT is 47.2 °, surface hydrophilicity raises, this is because the hydrophobic group in amphipathic ruthenium complex molecule is fixed to HOPG interface, hydrophilic group is exposed to surface, meanwhile, the change of contact angle to also demonstrate on HOPG amphipathic ruthenium complex monomolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after amphipathic ruthenium complex monomolecular film is modified that the present embodiment prepares: the HOPG after modified is anode, the HOPG substrate after to modification carries out the test of cyclic voltammetric to adopt cyclic voltammetry to judge.Experiment instrument is the AL660-C electrochemical analyser that BAS company of the U.S. produces, and optimum configurations is as follows: initial potential is 0V; High potential is 1.2V; Electronegative potential is 0V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50Hz; Multiplication factor 1; Sweep speed (unit is V/s) experimentally needs to be set as respectively: 0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in mensuration process
6solution (solvent is anhydrous MeCN) as electrolyte, dry 3h under vacuo before using, the HOPG substrate after modification as work electrode, Ag/AgNO
3as reference electrode, Pt line electrode as a comparison.First pass into the oxygen in 20 minutes nitrogen removal solution before experiment, the data of mensuration carry out current potential correction.Obtain the voltammogram of the HOPG substrate after modifying as shown in Figure 2, similar cyclic voltammetry curve is all obtained as can be seen from Figure 2 under different scanning speed, the reduction peak of central ion oxidation peak and part is there is near 0.42 ~ 0.45V, and compared to Figure 1 modified after the current value of HOPG substrate obviously increase, illustrate that the ruthenium complex molecular film prepared has good redox active.
Current value increases with the increase of sweep speed as can be seen from Figure 3, anode current ip
abe ip with the functional relation of scan velocity V
a=2.911 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-3.602 × 10
-6no matter V, be that anode current or cathode current all meet ip ∝ V relation, prove that ruthenium complex molecule is successfully assembled on HOPG substrate.The on-chip quantity of electric charge of HOPG and amount of coating calculate 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;
I
b: the electric current of B, A;
P
b: the voltage of B, V;
V: sweep speed, V/s.
（2）
Wherein, Г: amount of coating, mol/cm
2;
Q: the quantity of electric charge, C;
F:Faraday constant, 96485C/mol;
N: electron number;
A: contact area, 0.26cm
2.
According to formula (1) and (2) calculate through ruthenium complex monomolecular film modify after HOPG substrate on the quantity of electric charge be 9.653 × 10
-7c, amount of coating is 1.924 × 10
-11mol/cm
2.
Embodiment 2: the HOPG substrate of this amphipathic ruthenium complex monomolecular film directed modification is fixed in HOPG conductive substrates by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complex monomolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 15ml ultra-pure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complex of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultra-pure water and be settled to 30ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains the surface of new smooth conduction;
(3) the directed self assembly of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultra-pure water after 9h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
By testing the surface contact angle of the HOPG conductive substrates under different preparing processes, result is as follows: the contact angle on the HOPG surface after surface treatment is 61.9 °, the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 51.8 °, surface hydrophilicity raises, this is because the hydrophobic group in ruthenium complex molecule is fixed to HOPG interface, hydrophilic group is exposed to surface, and meanwhile, the change of contact angle to also demonstrate on HOPG ruthenium complex monomolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after ruthenium complex monomolecular film is modified that the present embodiment prepares: the HOPG after modified is anode, the HOPG substrate after to modification carries out the test of cyclic voltammetric to adopt cyclic voltammetry to judge.Experiment instrument is the AL660-C electrochemical analyser that BAS company of the U.S. produces, and optimum configurations is as follows: initial potential is 0V; High potential is 1.2V; Electronegative potential is 0V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50Hz; Multiplication factor 1; Sweep speed (unit is V/s) experimentally needs to be set as respectively: 0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in mensuration process
6solution (solvent is anhydrous MeCN) as electrolyte, dry 3h under vacuo before using, the HOPG substrate after modification as work electrode, Ag/AgNO
3as reference electrode, Pt line electrode as a comparison.First pass into the oxygen in 20 minutes nitrogen removal solution before experiment, the data of mensuration carry out current potential correction.Obtain the voltammogram of the HOPG substrate after modifying as shown in Figure 4, similar cyclic voltammetry curve is all obtained as can be seen from Figure 4 under different scanning speed, the reduction peak of central ion oxidation peak and part is there is near 0.42 ~ 0.45V, and compared to Figure 1 modified after the current value of HOPG substrate obviously increase, illustrate that the ruthenium complex molecular film prepared has good redox active.
Current value increases with the increase of sweep speed as can be seen from Figure 5, anode current ip
abe ip with the functional relation of scan velocity V
a=2.765 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-3.185 × 10
-6no matter V, be that anode current or cathode current all meet ip ∝ V relation, prove that ruthenium complex molecule is successfully assembled on HOPG substrate.The quantity of electric charge that I calculates on the HOPG substrate after ruthenium complex monomolecular film is modified according to formula (1) and (2) is 9.630 × 10
-7c, amount of coating is 1.920 × 10
-11mol/cm
2.
Embodiment 3: the HOPG substrate of this amphipathic ruthenium complex monomolecular film directed modification is fixed in HOPG conductive substrates by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complex monomolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 15ml ultra-pure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complex of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultra-pure water and be settled to 30ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains the surface of new smooth conduction;
(3) the directed self assembly of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultra-pure water after 12h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
By testing the surface contact angle of the HOPG conductive substrates under different preparing processes, result is as follows: the contact angle on the HOPG surface after surface treatment is 66.4 °, the surface contact angle of the HOPG after NW-TFT ruthenium complex monomolecular film is 54.8 °, surface hydrophilicity raises, this is because the hydrophobic group in ruthenium complex molecule is fixed to HOPG interface, hydrophilic group is exposed to surface, and meanwhile, the change of contact angle to also demonstrate on HOPG ruthenium complex monomolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after ruthenium complex monomolecular film is modified that the present embodiment prepares: the HOPG after modified is anode, the HOPG substrate after to modification carries out the test of cyclic voltammetric to adopt cyclic voltammetry to judge.Experiment instrument is the AL660-C electrochemical analyser that BAS company of the U.S. produces, and optimum configurations is as follows: initial potential is 0V; High potential is 1.2V; Electronegative potential is 0V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50Hz; Multiplication factor 1; Sweep speed (unit is V/s) experimentally needs to be set as respectively: 0.1,0.2,0.3,0.4,0.5.With 0.1MTBAPF in mensuration process
6solution (solvent is anhydrous MeCN) as electrolyte, dry 3h under vacuo before using, the HOPG substrate after modification as work electrode, Ag/AgNO
3as reference electrode, Pt line electrode as a comparison.First pass into the oxygen in 20 minutes nitrogen removal solution before experiment, the data of mensuration carry out current potential correction.Obtain the voltammogram of the HOPG substrate after modifying as shown in Figure 6, can find out from Fig. 6 and all obtain similar cyclic voltammetry curve different scanning speed, the reduction peak of central ion oxidation peak and part is there is near 0.42 ~ 0.45V, and compared to Figure 1 modified after the current value of HOPG substrate obviously increase, illustrate that the ruthenium complex molecular film prepared has good redox active.
Current value increases with the increase of sweep speed as can be seen from Figure 7, anode current ip
abe ip with the functional relation of scan velocity V
a=3.035 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-3.374 × 10
-6no matter V, be that anode current or cathode current all meet ip ∝ V relation, prove that ruthenium complex molecule is successfully assembled on HOPG substrate.The quantity of electric charge that I calculates on the HOPG substrate after ruthenium complex monomolecular film is modified according to formula (1) and (2) is 9.709 × 10
-7c, amount of coating is 1.935 × 10
-11mol/cm
2.
Embodiment 4: the HOPG substrate of this amphipathic ruthenium complex monomolecular film directed modification is fixed in HOPG conductive substrates by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complex monomolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 15ml ultra-pure water in clean beaker, PH to 11 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complex of 3.81mg is dissolved in above-mentioned solution, after regulating PH to 6 with HCl, add ultra-pure water and be settled to 30ml, obtain the amphipathic ruthenium complex solution of 49 μMs.
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains the surface of new smooth conduction.
(3) the directed self assembly of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultra-pure water after 8h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
Detecting the on-chip electric charge of HOPG after obtaining amphipathic ruthenium complex monomolecular film directed modification with reference to method in embodiment 1 is 9.673 × 10
-7c, amount of coating is 1.928 × 10
-11mol/cm
2.
Embodiment 5: the HOPG substrate of this amphipathic ruthenium complex monomolecular film directed modification is fixed in HOPG conductive substrates by the effect of non-covalent bond by the pyrenyl in amphipathic ruthenium complex molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complex monomolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 15ml ultra-pure water in clean beaker, PH to 12 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complex of 3.96mg is dissolved in above-mentioned solution, after regulating PH to 7 with HCl, add ultra-pure water and be settled to 30ml, obtain the amphipathic ruthenium complex solution of 51 μMs.
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains the surface of new smooth conduction.
(3) the directed self assembly of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultra-pure water after 11h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
The electric charge detected on the HOPG substrate after obtaining amphipathic ruthenium complex monomolecular film directed modification with reference to method in embodiment 1 is 9.693 × 10
-7c, amount of coating is 1.932 × 10
-11mol/cm
2.
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned execution mode, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (2)
1. the HOPG substrate of an amphipathic ruthenium complex monomolecular film directed modification, it is characterized in that: the pyrenyl in amphipathic ruthenium complex molecule is fixed in HOPG conductive substrates by the effect of non-covalent bond, form the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification, wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
。
2. the preparation method of the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification according to claim 1, is characterized in that concrete steps are as follows:
(1) preparation of amphipathic ruthenium complex solution: add ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 10 ~ 12, taking amphipathic ruthenium complex is dissolved in above-mentioned solution, and after regulating pH to 5 ~ 7 with HCl, obtained concentration is 49 ~ 51 μMs of amphipathic ruthenium complex solution;
(2) surface treatment of HOPG: by adhesive tape by being pressed in HOPG on the surface, then peel off, obtains new smooth conductive surface;
(3) NW-TFT of amphipathic ruthenium complex in HOPG conductive substrates: the HOPG substrate after surface treatment is immersed in amphipathic ruthenium complex solution, slight concussion removing bubble, after at room temperature flooding 6 ~ 12h, taking-up ultra-pure water cleans up rear inert gas and dries up, and namely obtains the HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification.
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|---|---|---|---|---|
| CN1306104A (en) * | 2000-03-25 | 2001-08-01 | 中国科学院长春应用化学研究所 | Process for preparing organic single-molecule-layer self-organized film on carbon substrate by electrochemical method |
| CN1584544A (en) * | 2004-06-10 | 2005-02-23 | 上海交通大学 | Method for forming nano gas layer on pyrolytic graphite surface based on alcohol-water substitution |
| CN201708038U (en) * | 2010-06-13 | 2011-01-12 | 曾日辉 | Dye-sensitized solar cell |
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