CN105669049B - The laminated film of binuclear ruthenium and graphene oxide - Google Patents
The laminated film of binuclear ruthenium and graphene oxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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Abstract
The invention discloses a kind of preparation method of the Electrostatic Self-Assembled Films based on binuclear ruthenium and graphene oxide.The film can be used as input signal by pH value of solution, bias and electron acceptor quinhydrones, regulate and control the size and switch of cathode photo current (cathodic photocurrent)/anode photoelectric current (anodic photocurrent), construction logic operation.
Description
Technical field
The present invention relates to film preparation, pH regulation and control photoelectric current switch and gate field, and in particular to graphene oxide and
The preparation method of one binuclear ruthenium Electrostatic Self-Assembled Films, the film can by change pH, bias and whether there is electronics to
Body quinhydrones switchs photoelectric current, forms logic gate device.
Background technology
For functional molecule apparatus, pH value of solution can be as the quick environmental stimuli for changing molecular property.With opening the light
In the compound of property, photoelectric property and the switchable [Ru(bpy)2(dppzi) of redox property receive much concern.These chemical combination
The change of the important photoelectricity of thing and redox property is relevant with the protonated/deprotonated balance of part.Contain benzimidazole
Part be preferable π donors, but poor π acceptors.In addition, benzimidazole has a free imino group N-H matter
Son, an outside in the protonated/deprotonated device that opens the light that can be seen as based on molecule of imidazole radicals ruthenium complex
Input signal.But the key of these complexs application is how these complexs to be firmly secured at into solid substrate or electrode
On.Electrostatic self-assembled technology has simple to operate, non-environmental-pollution, and can be any on the substrate of different shape and size
The advantages that assembling and easily regulation and control thickness, it has been widely used in solid substrate over-assemble ruthenium complex.As molecule meter
The important composition part of calculation machine, for converting Molecular Logic Gates of chemical, the electrical and optical input for detectable output,
As the active area of cross discipline research.At present, document largely had three basic logic door operations (AND, NOT, and
OR) and its functional molecular of more complicated logical operation report, and be mainly limited to solution, and fixed member is in solid substrate
On establish solid-state molecular logical device report seldom (Baitalik, S.；Dutta,S.；Biswas,P.；Flo rke,U.；
Bothe,E.；Nag,K.Eur.J.Inorg.Chem.,2010,570-588；Haga,M.A.；Takasugi,T.；Tomie,A.；
Ishizuya,M.；Yamada,T.；Hossain,M.D.；Inoue,M.Dalton Trans.,2003,2069–2079；Abe,
M.；Masuda,T.；Kondo,T.；Uosaki,K.；Sasaki,Y.Angew.Chem.,Int.Ed.,2005,44,416-419；
Maskus,M.；H.D.Langmuir 1996,12,4455-4462；Michi,T.；Abe,M.；Matsuno,J.；
Uosaki,K.；Sasaki,Y.Bull.Chem.Soc.Jpn.,2007,80,1368-1376；Zhou,W.；Ye,S.；Abe,M.；
Nishida,T.；Uosaki,K.；Osawa,M.；Sasaki,Y.Chem.Eur.J.,2005,11,5040-5054；Haga,M.；
Kobayashi,K.；Terada,K.Coord.Chem.Rev.,2007,251,2688-2701；Matsui,J.；Miyashita,
T.,Angew.Chem.Int.Ed.,2003,42,2272-2275；Matsui,J.；Mitsuishi,M.；Aoki,A.；
Miyashita,T.J.Am.Chem.Soc.,2004,126,3708–3709；Szacilowski,K.；Macyk,W.；
Stochel,G.J.Am.Chem.Soc.,2006,128,4550-4551；Beranek,R.Angew.Chem.Int.Ed.,
2008,47,1320-1322；Yasutomi,S.；Morita,T.；Imanishi,Y.；Kimura,S.Science 2004,
304,1944-1947), photoelectric current switch and the logic gate device for being particularly based on the pH inductions of Electrostatic Self-Assembled Films are more rare
(Wang Kezhi；Xue Longxin；Duan Zhiming, highly stable binuclear ruthenium evaporation membrane electrode and its preparation method and application, patent
Application number：2014106384062).
The content of the invention
The purpose of the present invention is open graphene oxide and a binuclear ruthenium in the hydrophilic group such as quartz substrate and ITO
The method of electrostatic self-assembled film forming on piece.
The purpose of the present invention is the open PhotoelectrochemicalProperties Properties by the film.
Another object of the present invention is open change pH value of solution and bias, the photoelectric current of energy switch film, can be formed more
Function logic door.
Technical scheme is as follows：
The binuclear ruthenium of application in this experiment is [(H2L2)Ru(HL1)Ru(bpy)2](ClO4)4, its cation portion
Divide [(H2L2)Ru(HL1)Ru(bpy)2]4+Structural formula be shown below：
The graphene oxide applied in the present invention is made according to document, is dissolved in water as follows with negative electrical charge, structure
Shown in formula, film forming can be assembled by electrostatic interaction with above-mentioned binuclear ruthenium.
The preparation method of the present invention is as follows：
Film is prepared before this, and quartz substrate is used to determine ultravioletvisible absorption, and indium oxide-tin oxide (ITO) substrate is used for
Light-metering electrical property.(i) substrate cleaned up is immersed in silylating reagent 12 hours (3- aminopropyl triethoxysilicanes
Alkane：Ethanol=1:19 volume ratios) so that substrate surface carries amino；(ii) substrate is immersed with being dried up after deionized water rinsing
To pH=3 hydrochloric acid solution 10 minutes so that the protonation of film surface amino groups is positively charged；(iii) after substrate being rinsed into drying, leaching
Steep in 1mg/ml graphene oxide water solution 15 minutes, electronegative graphene oxide Electrostatic Absorption to film surface；(iv)
Substrate is dipped into 1mM binuclear ruthenium acetonitrile solution 15 minutes again, the complex of positively charged passes through electrostatic phase interaction
With with graphene oxide film forming；Repeat step (iii) and (iv) can prepare multilayer film quartz or ITO/ (GO/RuRu) for n timesn.System
After standby film, film forming result is detected with ultraviolet-visible absorption spectroscopy.
Prepare BR cushioning liquid (0.04M glacial acetic acid, 0.04M boric acid, 0.04M phosphoric acid and 0.1M sodium sulphate).Different pH bars
The assay method of photoelectric current is under part：0.1M Na will be contained2SO4BR cushioning liquid as electrolyte solution, set bias as
0V, electrolyte solution pH is adjusted to obtain the photoelectric current numerical value of individual layer ITO/ (GO/RuRu) film under condition of different pH from 1 to 10.
In addition, also determining respectively under different pH environment (the hydrogen Kun containing 0.5mM), individual layer ITO/ (GO/RuRu) is thin when setting different biass
The photoelectric current numerical value of film.And then can construction logic gate device by experimental result.
Compared with prior art, advantage of the invention is that：
Instant invention overcomes electrochemistry in ruthenium complex-graphene oxide film aqueous solution and PhotoelectrochemicalProperties Properties are not steady enough
Fixed (Yang, W.；Zheng,Z.B.；Meng,T.T.；Wang,K.Z.Synergistically enhanced
photoelectrochemical properties of a layer-by-layer hybrid film based on
graphene oxide and a free terpyridyl grafted ruthenium complex,
J.Mater.Chem.A,2015,3(7),3441–3449；Meng,T.T.；Zheng,Z.B.；Wang,K.Z.Layer-by-
Layer Assembly of Graphene Oxide and a Ru(II)Complex and Significant
Photocurrent Generation Properties, Langmuir, 2013,29 (46), 14314-14320.), photoelectricity turns
Change the shortcomings such as efficiency is low, and be assembled in it by intermolecular electrostatic active force with graphene oxide by electrostatic self-assembled method
In ITO electrode, the stability of this film is assessed, studies photoelectric property of the film in different pH solution, and further grind
Study carefully the regulating and controlling effect of photoelectric respone of the outside stimulus (pH value of solution, bias, electron donor and acceptor) to film, and the reality by obtaining
Result is tested, is built using pH as input, photoelectric current is the multi-functional gate of output.
Brief description of the drawings
Fig. 1 is the preparation process of Electrostatic Self-Assembled Films.
Fig. 2 is (GO/RuRu) on quartz substraten(n=1-10) ultraviolet-visible absorption spectroscopy of plural layers.
Fig. 3 is the photoelectric current size of ITO/ (GO/RuRu) film under condition of different pH when bias is 0V.
Fig. 4 is bias when being 0V, photoelectric current spectrogram of ITO/ (GO/RuRu) films in pH=1 and 10.
Fig. 5 is the polarity of the photoelectric current under condition of different pH, measured under difference bias.
Fig. 6 is in the solution of the quinhydrones containing 0.5mM, and varying cyclically electrolyte pH=2 and 7 is obtained when 0V is biased
ITO/ (GO/RuRu) film photoelectric flow pattern map.
Fig. 7 is the AND logic gate built according to experimental result.
Fig. 8 is the OR gates built according to experimental result.
Fig. 9 is the YES gates built according to experimental result.
Embodiment
Below by embodiment, the present invention is further described.
Embodiment 1：Prepare (GO/RuRu)nElectrostatic Self-Assembled Films：
The number of assembling steps of film is as shown in Figure 1.Specifically completed by following several steps：(i) substrate cleaned up is immersed in
Silylating reagent (APTES：Ethanol=1:19 volume ratios) in 12 hours so that substrate surface carries
Amino；(ii) by substrate with being dried up after deionized water rinsing, it is immersed in pH=3 hydrochloric acid solution 10 minutes so that film surface ammonia
Base protonates positively charged；(iii) after substrate being rinsed into drying, it is dipped into 1mg/ml graphene oxide water solution 15 minutes,
Electronegative graphene oxide Electrostatic Absorption is to film surface；(iv) substrate is dipped into the solution of 1mM binuclear ruthenium again
In (acetonitrile：Water volume ratio=1:1) 15 minutes, the complex of positively charged passed through electrostatic interaction and graphene oxide film forming；
Repeat step (iii) and (iv) can prepare multilayer film.
Embodiment 2：The quartz substrate (GO/RuRu) of the different numbers of pliesn(n=1-10) uv-vis spectra of plural layers：
Uv-visible absorption spectra determines on UV-2600 spectrophotometry instrument, using quartz as substrate, every group
After installing a tunic, it is measured, and then obtains the ultraviolet-visible absorption spectra figure of film during the different numbers of plies (see Fig. 2).Read
Absorbance when taking the different numbers of plies at 510nm, obtain the linear relationship of the number of plies-absorbance.We can see that film forming from figure
It is uniform.200-265nm is the π-π of aromatic rings C-C in graphene oxide in spectrum*Transition absorption；Absworption peak at 510nm
Caused by metal in ruthenium complex to ligand charge shifts transition；The absworption peak at 280nm to 360nm places can be attributed to match somebody with somebody in vivo
π-π*Transition.It can be seen that absorbance linearly increases with the increase of the number of plies from Fig. 2 illustration, illustrate phase between layers
Interreaction force can be neglected.From the linear fit of this illustration according to formula：Γ=10-3D/ ε can obtain the coverage rate on film surface
For 1.66 × 10-10mol/cm2。
Embodiment 3：The measure of ITO/ (GO/RuRu) monofilm photoelectric property under condition of different pH
Photoelectric current measures in CHI electrochemical analysers, and using three-electrode system, ito thin film is working electrode
(0.28cm2), saturated calomel electrode is reference electrode, and platinum disk electrode is to electrode.The measure of photoelectric current is to contain 0.1M
Na2SO4BR cushioning liquid (0.04M glacial acetic acid, 0.04M boric acid, 0.04M phosphoric acid) be electrolyte solution.Sodium sulphate is to protect
The ionic strength of system is held, so as to reduce influence of the change of titration process ionic strength to test.Every in test process
A daylighting was carried out every 15 seconds, photoelectric current direction and size are read from collection of illustrative plates.
Fixed-bias transistor circuit is 0V, adjusts electrolyte solution pH to determine individual layer ITO/ (GO/RuRu) under condition of different pH from 1 to 10
The photoelectric current numerical value of film.As pH becomes big, caused cathode photo current significantly weakens (referring to Fig. 3), when pH was 10 time
Electric current is almost nil.Thus we can obtain photoelectric current switch as shown in Figure 4.Add 0.5mM's into electrolyte solution
Electron donor hydrogen Kun, continue to determine under different pH environment, individual layer ITO/ (GO/ are determined when setting different biass (- 0.4V~0.4V)
RuRu) the photoelectric current of film.The polarity of photoelectric current is read from collection of illustrative plates, as shown in figure 5, during different pH, by cathode photo current
Bias required for (cathodic photocurrent) is changed into anode photoelectric current (anodic photocurrent) is different.
It can also be seen that during fixed a certain bias, caused photoelectric current direction can change in different pH environment.For example bias is 0V
When, it is cathode photo current in pH=2, is converted to anode photoelectric current during pH=7.Circulation is tested, and obtains Fig. 6 institutes diagram
Spectrum, with pH change, photoelectric current direction changes and stability is preferable.
Embodiment 4：The structure of gate
According to above-mentioned experimental result, in bias -0.1V and 0V, pH=7, caused is cathode photo current.When to electricity
After adding 0.5mM electron donor hydrogen Kun in electrolyte solution, anode photoelectric current is produced in 0V.Using hydrogen Kun as input 1, bias
As input 2, anode photoelectric current can obtain AND logical operations as shown in Figure 7 (logic operation) as output.When
Using bias as 3 (for 0.1V as binary one, 0V is Binary Zero) of input, as input 4, (pH=7 binary ones, pH=6 bis- enter pH
0), anode photoelectric current can obtain OR gates as shown in Figure 8 to system as output signal.As shown in figure 9, when bias is 0V
YES logical operations can also be established, still using electron donor hydrogen Kun as input signal, but are believed using cathode photo current as output
Number.
Claims (5)
1. the laminated film of a kind of binuclear ruthenium and graphene oxide, it is characterised in that the film is utilized double-core ruthenium
Electrostatic interaction self assembly film forming between complex and graphene oxide, the binuclear ruthenium is [(H2L2)Ru(HL1)Ru
(bpy)2](ClO4)4, its cationic moiety [(H2L2)Ru(HL1)Ru(bpy)2]4+Structure be shown below：
。
2. film according to claim 1, it is characterised in that above-mentioned ruthenium complex and graphene oxide LBL self assembly exist
Quartz substrate through silanization treatment and on the hydrophilic substrate of ITO electro-conductive glass.
3. the preparation method of film, preparation process are as follows according to claim 2：
(i) substrate cleaned up is immersed in silylating reagent 12 hours so that substrate surface carries amino, the silanization
Reagent is that volume ratio is 1:19 APTES and the mixed liquor of ethanol；(ii) by substrate deionized water
Dried up after flushing, be immersed in pH=3 hydrochloric acid solution 10 minutes so that film surface amino groups protonate positively charged；(iii) by substrate
After rinsing drying, it is dipped into 1mg/ml graphene oxide water solution 15 minutes, electronegative graphene oxide Electrostatic Absorption
To film surface；(iv) substrate is dipped into again in the acetonitrile solution of 1mM binuclear ruthenium 15 minutes, the complex of positively charged
Pass through electrostatic interaction and graphene oxide film forming；Repeat step (iii) and (iv) can prepare multilayer film.
4. application of the film described in claim 1 in photoelectric current switch, it is characterised in that change pH and quinhydrones presence or absence,
Switch the size and Orientation of photoelectric current.
5. application of the film described in claim 1 in Tectonic logic door, it is characterised in that input, light are used as using pH and quinhydrones
Electric current forms YES, OR and AND logic gate as output.
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| CN107118235B (en) * | 2017-05-12 | 2019-05-14 | 北京师范大学 | Application of the near-infrared luminous ruthenium complex in cellular pH sensing |
| CN108409796B (en) * | 2018-03-06 | 2020-09-04 | 北京师范大学 | Application of near-infrared luminescent ruthenium complex in normal mouse organ imaging |
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