CN104446645A - Amphiphilic ruthenium complex monomolecular film directionally modified HOPG (highly oriented pyrolytic graphite) substrate and preparation method thereof - Google Patents
Amphiphilic ruthenium complex monomolecular film directionally modified HOPG (highly oriented pyrolytic graphite) substrate and preparation method thereof Download PDFInfo
- Publication number
- CN104446645A CN104446645A CN201410637336.9A CN201410637336A CN104446645A CN 104446645 A CN104446645 A CN 104446645A CN 201410637336 A CN201410637336 A CN 201410637336A CN 104446645 A CN104446645 A CN 104446645A
- Authority
- CN
- China
- Prior art keywords
- hopg
- ruthenium complexe
- substrate
- amphipathic ruthenium
- amphipathic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000010439 graphite Substances 0.000 title abstract description 6
- 229910002804 graphite Inorganic materials 0.000 title abstract description 6
- 239000012327 Ruthenium complex Substances 0.000 title abstract 3
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 115
- 229910052707 ruthenium Inorganic materials 0.000 claims description 115
- 230000004048 modification Effects 0.000 claims description 41
- 238000012986 modification Methods 0.000 claims description 40
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 19
- 239000012498 ultrapure water Substances 0.000 claims description 19
- 238000004381 surface treatment Methods 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 239000002390 adhesive tape Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000009514 concussion Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 32
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001338 self-assembly Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002408 directed self-assembly Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001075 voltammogram Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000002120 nanofilm Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000009467 reduction Effects 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
- 229910001369 Brass Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SAANWJOSHMCEKU-UHFFFAOYSA-N N#CC#N.[Ni] Chemical compound N#CC#N.[Ni] SAANWJOSHMCEKU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- AFEKSWFLEQJYBG-UHFFFAOYSA-N nickel oxalonitrile titanium Chemical compound [Ni].N#CC#N.[Ti] AFEKSWFLEQJYBG-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention discloses an amphiphilic ruthenium complex monomolecular film directionally modified HOPG (highly oriented pyrolytic graphite) substrate and a preparation method thereof. The HOPG substrate is prepared by immobilizing pyrenyl in amphiphilic ruthenium complex molecules on an HOPG conductive substrate via non-covalent bonds. The HOPG substrate and the preparation method have the beneficial effects that the method is simple to operate; an assembled layer is uniformly and fully modified on the HOPG substrate; the method can be operated by using simple containers at room temperature, without special conditions or equipment; the directionally modified HOPG substrate has excellent electrochemical activity; a prepared film has many advantages, such as good mechanical and chemical stability and controllability in thickness of the film.
Description
Technical field
The present invention relates to a kind of HOPG substrate and self-assembling method thereof of amphipathic ruthenium complexe unimolecular film directed modification, be specifically related to a kind of in HOPG conductive substrates the amphipathic ruthenium complexe of directed self-assembly form unimolecular 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 investigator 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 title complex that binding partner forms the octahedral structure of hexa-coordinate.Ruthenium complexe has good redox active, and its active centre generally includes the oxidation of central ion and the reduction of part.Ruthenium complexe 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(Highly Oriented Pyrolytic Graphite, 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 ceramic, has performance and other series of characteristics of metal and plastics concurrently, obtains widespread use at industrial sectors such as metallurgy, chemical industry, electric power and electronics, machinery, weaving and nuclear power.The most outstanding function of HOPG is the surface and the electric conductivity that have a unusual light.HOPG has laminate 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 complexe 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 complexe unimolecular 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 CN 102268715 A, have employed anodizing technology, by the brass after surface preparation after NaCl aqueous solution Anodic Oxidation, in the ethanolic soln 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 CN 102838626 A, with the supporting wall that the two carboxylic-acid 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 thermal 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 making method of high-selectivity semiconductor film " of CN 102376890 A, titanium cyanogen nickel is adopted to be sensitive membrane material, nitrogen-nitrogen dimethyl formamide is self-assembly solvent, on the travel path of SAW resonator surface or surface wave delay line, adopt self-assembling method titanium deposition cyanogen nickel film.The sensitive membrane of self-assembly by after thermal treatment to NO
2there is strong susceptibility and high selectivity.
At present, the unimolecular film self-assembly method of title 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 linkage or non covalent bond on the surface of electrode unimolecular layer.Self-assembled film molecular arrangement is tight in order, but assembling process is complicated, high to equipment requirements.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 complexe unimolecular film is modified, pyrenyl in amphipathic ruthenium complexe molecule is fixed in HOPG conductive substrates by the effect of non covalent bond, form the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification, wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
。
Another object of the present invention is to provide a kind of self-assembling method of HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification, and concrete steps are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add ultrapure water in clean beaker, with ammoniacal liquor modulation pH to 10 ~ 12, taking amphipathic ruthenium complexe is dissolved in above-mentioned solution, and after regulating pH to 5 ~ 7 with HCl, obtained concentration is 49 ~ 51 μMs of amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG substrate after surface treatment is immersed in amphipathic ruthenium complexe solution, slight concussion removing bubble, after at room temperature flooding 6 ~ 12h, taking-up ultrapure water cleans up rear rare gas element and dries up, and namely obtains the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification; The anode that HOPG substrate after this modification can be used as battery uses.
Described amphipathic ruthenium complexe obtains with reference to method in patent application 201410450980.5 " a kind of dye-sensitized solar cells amphipathic benzimidazoles ruthenium complexe 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 special conditions and equipment, HOPG substrate after directed modification has excellent electrochemical 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 complexe molecule and the surperficial effect by non covalent bond of HOPG, the pyrenyl section of ruthenium complexe molecule is fixed on HOPG interface, phosphate is exposed at electrode surface, thus realizing directed self-assembly ruthenium complexe unimolecular film in HOPG substrate, the surface of substrate is that wetting ability can continue to assemble other molecular films.
2, preparation method of the present invention obtains title complex assembled layers firm on electrode, and directed Iy self-assembled layer is evenly distributed in substrate, and has good electrochemical 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 plant and instrument and the special conditions 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 complexe unimolecular film directed modification that the embodiment of the present invention 1 prepares;
Fig. 3 is sweep velocity and the current relationship figure of the HOPG substrate after amphipathic ruthenium complexe unimolecular film directed modification that the embodiment of the present invention 1 prepares;
Fig. 4 is the voltammogram of the HOPG substrate after amphipathic ruthenium complexe unimolecular film directed modification that the embodiment of the present invention 2 prepares;
Fig. 5 is sweep velocity and the current relationship figure of the HOPG substrate after amphipathic ruthenium complexe unimolecular film directed modification that the embodiment of the present invention 2 prepares;
Fig. 6 is the voltammogram of the HOPG substrate after amphipathic ruthenium complexe unimolecular film directed modification that the embodiment of the present invention 3 prepares;
Fig. 7 is sweep velocity and the current relationship figure of the HOPG substrate after amphipathic ruthenium complexe unimolecular 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 complexe unimolecular film directed modification is fixed in HOPG conductive substrates by the effect of non covalent bond by the pyrenyl in amphipathic ruthenium complexe molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complexe unimolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add 15ml ultrapure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complexe of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultrapure water and be settled to 30ml, obtain the amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complexe solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultrapure water after 6h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complexe unimolecular 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 complexe unimolecular film of NW-TFT is 47.2 °, surface hydrophilicity raises, this is because the hydrophobic group in amphipathic ruthenium complexe 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 complexe unimolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after amphipathic ruthenium complexe unimolecular 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 0 V; Noble potential is 1.2V; Low potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Waiting time is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; Magnification 1; Sweep velocity (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 ionogen, dry 3h under vacuo before using, the HOPG substrate after modification as working 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 complexe molecular film prepared has good redox active.
Current value increases with the increase of sweep velocity as can be seen from Figure 3, anodic current ip
abe ip with the funtcional relationship of scan velocity V
a=2.911 × 10
-6v, cathodic current ip
bbe ip with the funtcional relationship of scan velocity V
b=-3.602 × 10
-6no matter V, be that anodic current or cathodic current all meet ip ∝ V relation, prove that ruthenium complexe 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 velocity, V/s.
（2）
Wherein, Г: amount of coating, mol/cm
2;
Q: the quantity of electric charge, C;
F:Faraday constant, 96485C/mol;
N: electronic number;
A: contact area, 0.26cm
2.
According to formula (1) and (2) calculate through ruthenium complexe unimolecular 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 complexe unimolecular film directed modification is fixed in HOPG conductive substrates by the effect of non covalent bond by the pyrenyl in amphipathic ruthenium complexe molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complexe unimolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add 15ml ultrapure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complexe of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultrapure water and be settled to 30ml, obtain the amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complexe solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultrapure water after 9h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complexe unimolecular 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 complexe unimolecular film is 51.8 °, surface hydrophilicity raises, this is because the hydrophobic group in ruthenium complexe 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 complexe unimolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after ruthenium complexe unimolecular 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 0 V; Noble potential is 1.2V; Low potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Waiting time is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; Magnification 1; Sweep velocity (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 ionogen, dry 3h under vacuo before using, the HOPG substrate after modification as working 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 complexe molecular film prepared has good redox active.
Current value increases with the increase of sweep velocity as can be seen from Figure 5, anodic current ip
abe ip with the funtcional relationship of scan velocity V
a=2.765 × 10
-6v, cathodic current ip
bbe ip with the funtcional relationship of scan velocity V
b=-3.185 × 10
-6no matter V, be that anodic current or cathodic current all meet ip ∝ V relation, prove that ruthenium complexe molecule is successfully assembled on HOPG substrate.The quantity of electric charge that I calculates on the HOPG substrate after ruthenium complexe unimolecular 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 complexe unimolecular film directed modification is fixed in HOPG conductive substrates by the effect of non covalent bond by the pyrenyl in amphipathic ruthenium complexe molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complexe unimolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add 15ml ultrapure water in clean beaker, PH to 10 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complexe of 3.89mg is dissolved in above-mentioned solution, after regulating PH to 5 with HCl, add ultrapure water and be settled to 30ml, obtain the amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complexe solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultrapure water after 12h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complexe unimolecular 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 complexe unimolecular film is 54.8 °, surface hydrophilicity raises, this is because the hydrophobic group in ruthenium complexe 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 complexe unimolecular film on successful NW-TFT.
The electrochemical property test of the HOPG after ruthenium complexe unimolecular 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 0 V; Noble potential is 1.2V; Low potential is 0 V; Initial stage scanning is Poaitive; Scanning times is 6 times; Waiting time is 3 ~ 5 s; Sensitivity is chosen as 10 μ A; Filtering parameter is 50 Hz; Magnification 1; Sweep velocity (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 ionogen, dry 3h under vacuo before using, the HOPG substrate after modification as working 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 complexe molecular film prepared has good redox active.
Current value increases with the increase of sweep velocity as can be seen from Figure 7, anodic current ip
abe ip with the funtcional relationship of scan velocity V
a=3.035 × 10
-6v, cathodic current ip
bbe ip with the funtcional relationship of scan velocity V
b=-3.374 × 10
-6no matter V, be that anodic current or cathodic current all meet ip ∝ V relation, prove that ruthenium complexe molecule is successfully assembled on HOPG substrate.The quantity of electric charge that I calculates on the HOPG substrate after ruthenium complexe unimolecular 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 complexe unimolecular film directed modification is fixed in HOPG conductive substrates by the effect of non covalent bond by the pyrenyl in amphipathic ruthenium complexe molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
；
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complexe unimolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add 15ml ultrapure water in clean beaker, PH to 11 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complexe of 3.81mg is dissolved in above-mentioned solution, after regulating PH to 6 with HCl, add ultrapure water and be settled to 30ml, obtain the amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complexe solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultrapure water after 8h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification.
Detecting the on-chip electric charge of HOPG after obtaining amphipathic ruthenium complexe unimolecular 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 complexe unimolecular film directed modification is fixed in HOPG conductive substrates by the effect of non covalent bond by the pyrenyl in amphipathic ruthenium complexe molecule to be formed, and wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
The self-assembling method concrete steps of the HOPG substrate of above-mentioned amphipathic ruthenium complexe unimolecular film directed modification are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add 15ml ultrapure water in clean beaker, PH to 12 is regulated with ammoniacal liquor, taking the amphipathic ruthenium complexe of 3.96mg is dissolved in above-mentioned solution, after regulating PH to 7 with HCl, add ultrapure water and be settled to 30ml, obtain the amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG after surface treatment to be immersed in amphipathic ruthenium complexe solution front outwardly, slight concussion removing bubble, at room temperature flood and to take out HOPG substrate ultrapure water after 11h and clean up rear nitrogen and dry up, namely obtain the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification.
The electric charge detected on the HOPG substrate after obtaining amphipathic ruthenium complexe unimolecular 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 embodiment, 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 complexe unimolecular film directed modification, it is characterized in that: the pyrenyl in amphipathic ruthenium complexe molecule is fixed in HOPG conductive substrates by the effect of non covalent bond, form the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification, wherein the chemical structural formula of amphipathic ruthenium complexe is as follows:
。
2. the preparation method of the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification according to claim 1, is characterized in that concrete steps are as follows:
(1) preparation of amphipathic ruthenium complexe solution: add ultrapure water in clean beaker, with ammoniacal liquor modulation pH to 10 ~ 12, taking amphipathic ruthenium complexe is dissolved in above-mentioned solution, and after regulating pH to 5 ~ 7 with HCl, obtained concentration is 49 ~ 51 μMs of amphipathic ruthenium complexe 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 complexe in HOPG conductive substrates: the HOPG substrate after surface treatment is immersed in amphipathic ruthenium complexe solution, slight concussion removing bubble, after at room temperature flooding 6 ~ 12h, taking-up ultrapure water cleans up rear rare gas element and dries up, and namely obtains the HOPG substrate of amphipathic ruthenium complexe unimolecular film directed modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410637336.9A CN104446645B (en) | 2014-11-13 | 2014-11-13 | HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410637336.9A CN104446645B (en) | 2014-11-13 | 2014-11-13 | HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104446645A true CN104446645A (en) | 2015-03-25 |
| CN104446645B CN104446645B (en) | 2016-02-24 |
Family
ID=52893489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410637336.9A Active CN104446645B (en) | 2014-11-13 | 2014-11-13 | HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104446645B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20020146556A1 (en) * | 2001-04-04 | 2002-10-10 | Ga-Tek Inc. (Dba Gould Electronics Inc.) | Resistor foil |
| 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 |
| JP2011051801A (en) * | 2009-08-31 | 2011-03-17 | National Institute For Materials Science | Method for producing graphene film |
-
2014
- 2014-11-13 CN CN201410637336.9A patent/CN104446645B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20020146556A1 (en) * | 2001-04-04 | 2002-10-10 | Ga-Tek Inc. (Dba Gould Electronics Inc.) | Resistor foil |
| 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 |
| JP2011051801A (en) * | 2009-08-31 | 2011-03-17 | National Institute For Materials Science | Method for producing graphene film |
| CN201708038U (en) * | 2010-06-13 | 2011-01-12 | 曾日辉 | Dye-sensitized solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104446645B (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jang et al. | An unconventional route to high-efficiency dye-sensitized solar cells via embedding graphitic thin films into TiO2 nanoparticle photoanode | |
| Kim et al. | General strategy for fabricating transparent TiO2 nanotube arrays for dye-sensitized photoelectrodes: illumination geometry and transport properties | |
| Umar | Growth of comb-like ZnO nanostructures for dye-sensitized solar cells applications | |
| Yang et al. | Three-dimensional photonic crystal fluorinated tin oxide (FTO) electrodes: synthesis and optical and electrical properties | |
| Liu et al. | Black anatase TiO2 nanotubes with tunable orientation for high performance supercapacitors | |
| Chandiran et al. | Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells | |
| Sookhakian et al. | Layer-by-layer electrodeposited reduced graphene oxide-copper nanopolyhedra films as efficient platinum-free counter electrodes in high efficiency dye-sensitized solar cells | |
| Sun et al. | Conformal growth of anodic nanotubes for dye-sensitized solar cells: part I. planar electrode | |
| Punnoose et al. | Highly catalytic nickel sulfide counter electrode for dye-sensitized solar cells | |
| Zukalova et al. | Electrochemical doping of compact TiO2 thin layers | |
| Loewenstein et al. | Textile‐Compatible Substrate Electrodes with Electrodeposited ZnO—A New Pathway to Textile‐Based Photovoltaics | |
| Bunea et al. | Micropatterned carbon-on-quartz electrode chips for photocurrent generation from thylakoid membranes | |
| Wang et al. | Design, synthesis and electrocatalytic properties of coaxial and layer-tunable MoS 2 nanofragments/TiO 2 nanorod arrays | |
| CN106967979B (en) | A kind of modified BiFeO of phosphoric acid cobalt catalyst3Film photoelectric electrode and preparation method thereof | |
| Peng et al. | BiOCl nanorings with co-exposed (110)/(001) facets for photocatalytic degradation of organic dyes | |
| Ni et al. | Efficiency improvement of TiO2 nanowire arrays based dye-sensitized solar cells through further enhancing the specific surface area | |
| CN102732921B (en) | Ionic liquid electrodeposition method for preparing three-dimensional ordered macroporous silicon-germanium and germanium-aluminum heterogeneous thin-film material | |
| Huang et al. | Photoelectrochemical properties of ZnO/BiVO4 nanorod arrays prepared through a facile spin-coating deposition route | |
| CN109560148A (en) | A kind of nano generator and preparation method based on nano structure membrane electrode | |
| Mu et al. | Solvent-controlled formation and photoelectrochemical sensing properties of 3-dimensional TiO 2 nanostructures | |
| Chen et al. | Photoelectrochemical properties of electrostatically self-assembled multilayer films formed by a cobalt complex and graphene oxide | |
| CN107195788A (en) | The perovskite thin film preparation method synthesized based on the step of electrochemistry two | |
| CN104446645B (en) | HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof | |
| CN104587847A (en) | Electric functional membrane and preparation method thereof | |
| Zhao et al. | Molten Salt Synthesis of Mg-Doped Ta3N5 Nanoparticles with Optimized Surface Properties for Enhanced Photocatalytic Hydrogen Evolution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |