CN104465098A - ITO substrate modified by amphiphilic ruthenium complex monomolecular film and preparation method of ITO substrate - Google Patents
ITO substrate modified by amphiphilic ruthenium complex monomolecular film and preparation method of ITO substrate Download PDFInfo
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- CN104465098A CN104465098A CN201410636936.3A CN201410636936A CN104465098A CN 104465098 A CN104465098 A CN 104465098A CN 201410636936 A CN201410636936 A CN 201410636936A CN 104465098 A CN104465098 A CN 104465098A
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 116
- 239000000758 substrate Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000012986 modification Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 52
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 40
- 239000012498 ultrapure water Substances 0.000 claims description 40
- 238000004140 cleaning Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 230000009514 concussion Effects 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002120 nanofilm Substances 0.000 abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000002094 self assembled monolayer Substances 0.000 description 6
- 239000013545 self-assembled monolayer Substances 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- 238000001075 voltammogram Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
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- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920013674 Lumarith Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- XISQJDPDCQYNKD-UHFFFAOYSA-N [Ru].N1=CNC2=C1C=CC=C2 Chemical compound [Ru].N1=CNC2=C1C=CC=C2 XISQJDPDCQYNKD-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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Abstract
The invention discloses an ITO substrate modified by an amphiphilic ruthenium complex monomolecular film and a preparation method of the ITO substrate. The ITO substrate is manufactured by fixing hydroxyl radicals in amphiphilic ruthenium complex molecules to ITO conducting glass under the action of covalent bonds. According to the method, operation is simple, modification is uniform and sufficient, operation can be conducted by using a simple container at room temperature, no special condition or equipment is needed, and the modified ITO substrate has excellent optical and electrochemical performance. Besides, under the condition that a small amount of water exists, the desorption performance of the ruthenium molecular film can still be greatly reduced, and therefore the water-resistant stability of the substrate is improved.
Description
Technical field
The present invention relates to a kind of ITO substrate and self-assembling method thereof of amphipathic ruthenium complex monomolecular film modification, be specifically related to a kind of method of self assembly amphipathic ruthenium complex formation monomolecular film on ITO electro-conductive glass and obtained modified ITO substrate, belong to molecular self-assembling chemical field.
Background technology
Self-assembled film has attracted the common concern of the scientist of numerous different field, different subject in recent years, and this and its critical role residing in scientific research and practical application is closely related.Due to the microminiaturization increasingly of electronic device, self-assembled film will play an important role in the preparation of microelectronic component.
The preparations and applicatio of self-assembled film is the Main way of current self assembly area research.Molecular self-assembled monolayer, particularly self-assembled monolayer are the fields of molecular self-assembling most study, and are widely used.Self-assembled monolayer has practical application at numerous areas such as electronic instrument manufacture, plastic shaping, lumarith researchs.Self-assembled monolayer is by containing free-moving end group, and the organic molecule of such as mercaptan, amino etc., to electrode surface reforming, imparts the function that electrode surface is new.In addition molecular self-assembling is mainly used in the biomolecule such as enzyme, protein self-assembled film in bioscience.These biomolecule self-assembled films are widely used in biology sensor, molecular device, efficient catalytic material, biomaterial for medical purpose field.
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.Covalence key closes and utilizes the covalent bond between key and key to carry out ordered fabrication, and the main molecule containing hydroxyl or carboxyl that adopts forms self assembled monolayer at electrode surface.
The research of the domestic method to the amphipathic ruthenium complex monomolecular film of self assembly on ITO electro-conductive glass at present have not been reported.The self-assembling method of disclosed molecular film mainly contains:
Publication number is China's application disclosed " a kind of electroluminescent molecular self-assembling body and application thereof " of CN 102093570 A, disclose a kind of electroluminescent molecular self-assembling body and application thereof, in cosolvent, formed the macromolecular complex thing of the intersegmental pairing of chain by non-covalent interaction.Conventional spin-coating method is adopted to carry out the preparation of electroluminescent device again.
Publication number is in China's application disclosed " a kind of liquid phase self-assembling method prepares the method for bismuth ferrite function film on the glass substrate " of CN 101659520 A, adopt liquid phase self-assembled monolayer film method, under ultraviolet equipment is auxiliary, activation is carried out to glass substrate, and on the glass substrate of activate induced growth BiFeO
3.
Publication number is in China's application disclosed " preparation method of self-assembling ultrathin polymer film " of CN 1403494 A, synthesizes membrane material by radical copolymerization, has utilized self-assembling technique to prepare to have the thin polymer film of various surface nature.Preparation process is simple, and the polymer ultra-thin film of preparation has antifriction, anti-wear effect.
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 on the surface of electrode by covalent bond the orderly monolayer of spontaneous height of formation.Self-assembled film molecules align is tight in order, and under ultralow temperature, UHV condition, keep stable, assembling process is complicated, high and easily come off from substrate by molecular film when water and organic solvent dissolution to equipment requirement.Thus a kind of self assembling process of design invention is simple and to form the molecular film method that stability is high, water-resistance is strong very necessary.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides the ITO substrate that a kind of amphipathic ruthenium complex monomolecular film is modified, hydroxyl in amphipathic ruthenium complex molecule is fixed on ITO electro-conductive glass by the effect of covalent bond, form the ITO substrate that amphipathic ruthenium complex monomolecular film is modified, wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
。
Another object of the present invention is to provide the self-assembling method of the ITO substrate that a kind of amphipathic ruthenium complex monomolecular film is modified, 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 solution, and after regulating pH to 5 ~ 7 with HCl, obtained concentration is 49 ~ 51 μMs of amphipathic ruthenium complex solution;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution ultrasonic process 20 ~ 60min under the frequency of 30 ~ 50KHz being added with washing agent, with ultra-pure water cleaning after ultrasonic cleaning, inert gas dries up;
(3) hydrophilic treated of ITO conductive glass surface: the ITO electro-conductive glass after cleaning is immersed in RCA solution, move in water-bath filled with hot water after slight concussion removing bubble, take out ITO electro-conductive glass ultra-pure water after being heated to 90 ~ 120 DEG C of process 0.5 ~ 2h to clean, inert gas dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated is immersed in amphipathic ruthenium complex solution, slight concussion removing bubble, after at room temperature flooding 3 ~ 6h, taking-up ultra-pure water cleans up rear inert gas and dries up, and namely obtains the ITO substrate that amphipathic ruthenium complex monomolecular film is modified; The anode that ITO substrate after this modification can be used as battery uses.
Described RCA solution is ammoniacal liquor, H
2o
2with the solution that the ratio of ultra-pure water 1:1:5 is by volume obtained by mixing.
Described washing agent is any chemical or the aqueous cleaning agent of conventional commercial, uses RT-808 ultrasonic cleaning agent in the present invention.
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, modify evenly fully, simple receptacle is at room temperature used to operate, without the need to specific condition and equipment, ITO electro-conductive glass after modified has excellent optical, electrical chemical property, and under a small amount of water existent condition, still significantly can reduce the solution absorption of ruthenium molecular film, improve the water resistant stability of substrate.
The invention has the beneficial effects as follows:
1, the hydroxyl in this amphipathic ruthenium complex molecule and the surperficial effect by covalent bond of ITO, the hydrophilic group of ruthenium complex molecule is fixed on ITO surface, hydrophobic group is exposed on film surface, make film surface presentation hydrophobicity, even if make under a small amount of water existent condition, still significantly can reduce the solution absorption of ruthenium monomolecular film, improve the water resistant stability of substrate.
2, the ITO substrate after amphipathic ruthenium complex monomolecular film is modified, as anode, has excellent optical, electrical chemical property, can be used for the fields such as DSSC.
3, the present invention at room temperature uses simple receptacle to operate, and without the need to specific condition and equipment, preparation method is simple to operate, and preparation cost is low, and raw material is easy to get, and the ruthenium monomolecular film modification obtained is evenly abundant and reproducible.
Accompanying drawing explanation
Fig. 1 is the voltammogram of the ITO substrate after amphipathic ruthenium complex monomolecular film is modified that the embodiment of the present invention 1 prepares;
Fig. 2 is sweep speed and the current relationship figure of the ITO substrate after amphipathic ruthenium complex monomolecular film is modified that the embodiment of the present invention 1 prepares;
Fig. 3 is the voltammogram of the ITO substrate after ruthenium complex monomolecular film is modified that the embodiment of the present invention 2 prepares;
Fig. 4 is sweep speed and the current relationship figure of the ITO substrate after ruthenium complex monomolecular film is modified that the embodiment of the present invention 2 prepares;
Fig. 5 is the voltammogram of the ITO substrate after ruthenium complex monomolecular film is modified that the embodiment of the present invention 3 prepares;
Fig. 6 is sweep speed and the current relationship figure of the ITO substrate after ruthenium complex monomolecular film is modified 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 ITO substrate that this amphipathic ruthenium complex monomolecular film is modified is fixed on ITO electro-conductive glass by the effect of covalent bond by the hydroxyl 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 ITO substrate that above-mentioned amphipathic ruthenium complex monomolecular film is modified are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 20ml ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 10, taking the amphipathic ruthenium complex of 5.18mg is dissolved in solution, after regulating pH to 5 with HCl, add ultra-pure water and be settled to 40ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution being added with washing agent, clean 30min under the frequency of 30KHz after, with ultra-pure water cleaning, nitrogen dries up;
(3) hydrophilic treated of ITO conductive glass surface: by ammoniacal liquor, H
2o
2with the ratio mixed preparing RCA solution of ultra-pure water 1:1:5 by volume, ITO electro-conductive glass after cleaning to be immersed in RCA solution front outwardly, move in water-bath filled with hot water after slight concussion removing bubble, after 90 DEG C of heating 0.5h, taking-up ultra-pure water is cleaned, and nitrogen dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated to be immersed in ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood taking-up ultra-pure water after 3h to clean up rear nitrogen and dry up, namely obtain the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
By testing the surface contact angle of the ITO electro-conductive glass under different preparing processes, result is as follows: the contact angle of the ITO substrate surface after cleaning is 86.3 °, illustrates that clean ITO surface is for hydrophobicity; The contact angle of the ITO substrate surface after surface hydrophilic process is 66.4 °, demonstrates the hydrophily that hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle assembling the ITO substrate after amphipathic ruthenium complex monomolecular film is 81.0 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complex molecule is fixed to ITO interface, hydrophobic group is exposed to surface, the ITO substrate surface after assembling ruthenium complex monomolecular film is made to present hydrophobicity, meanwhile, the change of contact angle also demonstrates on ITO and successfully assembles upper amphipathic ruthenium complex monomolecular film.
The electrochemical property test of the ITO substrate after amphipathic ruthenium complex monomolecular film is modified that the present embodiment prepares: using the ITO substrate after modified as anode, adopts cyclic voltammetry to judge to carry out ITO substrate after modifying the test of cyclic voltammetric.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 0 V; High potential is 1.2V; Electronegative potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; 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 0.1 MTBAPF in mensuration process
6solution (solvent is anhydrous MeCN) as electrolyte, dry 3h under vacuo before using, the ITO 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 ITO substrate after modifying as shown in Figure 1, similar cyclic voltammetry curve is all obtained as can be seen from Figure 1 under different scanning speed, near 0.48V, there is the reduction peak of central ion oxidation peak and part, 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 2, anode current ip
abe ip with the functional relation of scan velocity V
a=4.266 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-4.684 × 10
-6no matter V, be that anode current or cathode current all meet ip ∝ V relation, prove that amphipathic ruthenium complex molecule is successfully assembled on ITO substrate.The on-chip quantity of electric charge of ITO 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.
1.42 × 10 according to the quantity of electric charge that formula (1) and (2) calculate on the ito substrate after amphipathic ruthenium complex monomolecular film is modified
-6c, amount of coating is 2.82 × 10
-11mol/cm
2.
Embodiment 2: the ITO substrate that this amphipathic ruthenium complex monomolecular film is modified is fixed on ITO electro-conductive glass by the effect of covalent bond by the hydroxyl 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 ITO substrate that above-mentioned amphipathic ruthenium complex monomolecular film is modified are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 20ml ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 10, taking the amphipathic ruthenium complex of 5.18mg is dissolved in solution, after regulating pH to 5 with HCl, add ultra-pure water and be settled to 40ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution being added with washing agent, clean 30min under the frequency of 35KHz after, after cleaning 40min, with ultra-pure water cleaning, nitrogen dries up;
(3) hydrophilic treated of ITO conductive glass surface: by ammoniacal liquor, H
2o
2with the ratio mixed preparing RCA solution of ultra-pure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, and after 100 DEG C of heating 1h, take out ITO substrate ultra-pure water clean, nitrogen dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated to be immersed in ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out ITO substrate ultra-pure water after 4h and clean up rear nitrogen and dry up, namely obtain the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
By testing the surface contact angle of the ITO electro-conductive glass under different preparing processes, result is as follows: the contact angle of the ITO substrate surface after cleaning is 87.6 °, illustrates that clean ITO surface is for hydrophobicity; The contact angle of the ITO substrate surface after surface hydrophilic process is 66.6 °, demonstrates the hydrophily that hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle assembling the ITO substrate after amphipathic ruthenium complex monomolecular film is 81.5 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complex molecule is fixed to ITO interface, hydrophobic group is exposed to surface, the ITO substrate surface after assembling ruthenium complex monomolecular film is made to present hydrophobicity, meanwhile, the change of contact angle also demonstrates on ITO and successfully assembles upper ruthenium complex monomolecular film.
The electrochemical property test of the ITO substrate after amphipathic ruthenium complex monomolecular film is modified that the present embodiment prepares: the ITO substrate after modified is anode, the ITO 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 0 V; High potential is 1.2V; Electronegative potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; 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 ITO 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 ITO substrate after modifying as shown in Figure 3, can find out from Fig. 3 and all obtain similar cyclic voltammetry curve different scanning speed, near 0.48V, there is the reduction peak of central ion oxidation peak and part, 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 4, anode current ip
abe ip with the functional relation of scan velocity V
a=4.90 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-5.31 × 10
-6no matter V, be that anode current or cathode current all meet ip ∝ V relation, prove that amphipathic ruthenium complex molecule is successfully assembled on ITO substrate.According to embodiment 1 Chinese style (1) and (2) calculate through ruthenium complex monomolecular film modify after ito substrate on the quantity of electric charge be 1.36 × 10
-6c, amount of coating is 2.72 × 10
-11mol/cm
2.
Embodiment 3: the ITO substrate that this amphipathic ruthenium complex monomolecular film is modified is fixed on ITO electro-conductive glass by the effect of covalent bond by the hydroxyl 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 ITO substrate that above-mentioned amphipathic ruthenium complex monomolecular film is modified are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 20ml ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 10, taking the amphipathic ruthenium complex of 5.18mg is dissolved in solution, after regulating pH to 5 with HCl, add ultra-pure water and be settled to 40ml, obtain the amphipathic ruthenium complex solution of 50 μMs;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution being added with washing agent, clean 30min under the frequency of 40KHz after, after cleaning 50min, with ultra-pure water cleaning, nitrogen dries up;
(3) hydrophilic treated of ITO conductive glass surface: by ammoniacal liquor, H
2o
2with the ratio mixed preparing RCA solution of ultra-pure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, and after 110 DEG C of heating 1.5h, take out ITO substrate ultra-pure water clean, nitrogen dries up.
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated to be immersed in ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out ITO substrate ultra-pure water after 5h and clean up rear nitrogen and dry up, namely obtain the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
By testing the surface contact angle of the ITO electro-conductive glass under different preparing processes, result is as follows: the contact angle of the ITO substrate surface after cleaning is 87.6 °, illustrates that clean ITO surface is for hydrophobicity; The contact angle of the ITO substrate surface after surface hydrophilic process is 61.9 °, demonstrates the hydrophily that hydrophilic treatment method of the present invention improves ITO surface; The surface contact angle of the ITO substrate after assembling ruthenium complex monomolecular film is 80.9 °, surface hydrophilicity reduces, this is because the hydrophilic group in ruthenium complex molecule is fixed to ITO interface, hydrophobic group is exposed to surface, the ITO substrate surface after assembling ruthenium complex monomolecular film is made to present hydrophobicity, meanwhile, the change of contact angle also demonstrates on ITO and successfully assembles upper ruthenium complex monomolecular film.
The electrochemical property test of the ITO substrate after ruthenium complex monomolecular film is modified that the present embodiment prepares: the ITO substrate after modified is anode, the ITO 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 0 V; High potential is 1.2V; Electronegative potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Stand-by period is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; 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 ITO 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 ITO substrate after modifying as shown in Figure 5, can find out from Fig. 5 and all obtain similar cyclic voltammetry curve different scanning speed, near 0.48V, there is the reduction peak of central ion oxidation peak and part, 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 6, anode current ip
abe ip with the functional relation of scan velocity V
a=4.62 × 10
-6v, cathode current ip
bbe ip with the functional relation of scan velocity V
b=-4.71 × 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 ITO substrate.According to embodiment 1 Chinese style (1) and (2) calculate through ruthenium complex monomolecular film modify after ito substrate on the quantity of electric charge be 1.50 × 10
-6c, amount of coating is 2.89 × 10
-11mol/cm
2.
Embodiment 4: the ITO substrate that this amphipathic ruthenium complex monomolecular film is modified is fixed on ITO electro-conductive glass by the effect of covalent bond by the hydroxyl in amphipathic ruthenium complex molecule to be formed;
The self-assembling method concrete steps of the ITO substrate that above-mentioned amphipathic ruthenium complex monomolecular film is modified are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 20ml ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 11, taking the amphipathic ruthenium complex of 5.078mg is dissolved in solution, after regulating pH to 7 with HCl, add ultra-pure water and be settled to 40ml, obtain the amphipathic ruthenium complex solution of 49 μMs;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution being added with washing agent, clean 30min under the frequency of 45KHz after, after cleaning 20min, with ultra-pure water cleaning, nitrogen dries up;
(3) hydrophilic treated of ITO conductive glass surface: by ammoniacal liquor, H
2o
2with the ratio mixed preparing RCA solution of ultra-pure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, and after 120 DEG C of heating 0.5h, take out ITO substrate ultra-pure water clean, nitrogen dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated to be immersed in ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out ITO substrate ultra-pure water after 6h and clean up rear nitrogen and dry up, namely obtain the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
The quantity of electric charge detected on the ito substrate after obtaining the modification of amphipathic ruthenium complex monomolecular film with reference to method in embodiment 1 is 1.42 × 10
-6c, amount of coating is 2.84 × 10
-11mol/cm
2.
Embodiment 5: the ITO substrate that this amphipathic ruthenium complex monomolecular film is modified is fixed on ITO electro-conductive glass by the effect of covalent bond by the hydroxyl in amphipathic ruthenium complex molecule to be formed;
The self-assembling method concrete steps of the ITO substrate that above-mentioned amphipathic ruthenium complex monomolecular film is modified are as follows:
(1) preparation of amphipathic ruthenium complex solution: add 20ml ultra-pure water in clean beaker, with ammoniacal liquor modulation pH to 12, taking the amphipathic ruthenium complex of 5.285mg is dissolved in solution, after regulating pH to 6 with HCl, add ultra-pure water and be settled to 40ml, obtain the amphipathic ruthenium complex solution of 51 μMs;
(2) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution being added with washing agent, clean 30min under the frequency of 50KHz after, after cleaning 60min, with ultra-pure water cleaning, nitrogen dries up;
(3) hydrophilic treated of ITO conductive glass surface: by ammoniacal liquor, H
2o
2with the ratio mixed preparing RCA solution of ultra-pure water in 1:1:5, ITO substrate to be immersed in RCA solution front outwardly, slight concussion is gone out after bubble and is moved in water-bath filled with hot water, and after 100 DEG C of heating 2h, take out ITO substrate ultra-pure water clean, nitrogen dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated to be immersed in ruthenium complex solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out ITO substrate ultra-pure water after 3h and clean up rear nitrogen and dry up, namely obtain the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
The electric charge detected on the ito substrate after obtaining the modification of amphipathic ruthenium complex monomolecular film with reference to method in embodiment 1 is 1.44 × 10
-6c, amount of coating is 2.88 × 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 (3)
1. the ITO substrate of an amphipathic ruthenium complex monomolecular film modification, it is characterized in that: the hydroxyl in amphipathic ruthenium complex molecule is fixed on ITO electro-conductive glass by the effect of covalent bond, form the ITO substrate that amphipathic ruthenium complex monomolecular film is modified, wherein the chemical structural formula of amphipathic ruthenium complex is as follows:
。
2. the preparation method of the ITO substrate of amphipathic ruthenium complex monomolecular film 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) cleaning of ITO electro-conductive glass: ITO electro-conductive glass is placed in the aqueous solution ultrasonic process 20 ~ 60min under the frequency of 30 ~ 50KHz being added with washing agent, with ultra-pure water cleaning after ultrasonic cleaning, inert gas dries up;
(3) hydrophilic treated of ITO conductive glass surface: the ITO electro-conductive glass after cleaning is immersed in RCA solution, move in water-bath filled with hot water after slight concussion removing bubble, take out ITO electro-conductive glass ultra-pure water after being heated to 90 ~ 120 DEG C of process 0.5 ~ 2h to clean, inert gas dries up;
(4) assembling of amphipathic ruthenium complex on ITO electro-conductive glass: the ITO electro-conductive glass after hydrophilic treated is immersed in amphipathic ruthenium complex solution, slight concussion removing bubble, after at room temperature flooding 3 ~ 6h, taking-up ultra-pure water cleans up rear inert gas and dries up, and namely obtains the ITO substrate that amphipathic ruthenium complex monomolecular film is modified.
3. the preparation method of the ITO substrate of amphipathic ruthenium complex monomolecular film modification according to claim 2, is characterized in that: RCA solution is ammoniacal liquor, H
2o
2with the solution that the ratio of ultra-pure water 1:1:5 is by volume obtained by mixing.
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| CN111073007A (en) * | 2018-10-22 | 2020-04-28 | 北京工商大学 | Preparation of organic polymer and ruthenium coordination polymer hybrid film and photoelectric property thereof |
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| CN1403494A (en) * | 2002-09-15 | 2003-03-19 | 中国科学院兰州化学物理研究所 | Prepn of self-assembled superthin polymer film |
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