CN101386471A - Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine - Google Patents
Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine Download PDFInfo
- Publication number
- CN101386471A CN101386471A CNA2008100716425A CN200810071642A CN101386471A CN 101386471 A CN101386471 A CN 101386471A CN A2008100716425 A CNA2008100716425 A CN A2008100716425A CN 200810071642 A CN200810071642 A CN 200810071642A CN 101386471 A CN101386471 A CN 101386471A
- Authority
- CN
- China
- Prior art keywords
- organic
- composite film
- transition metal
- polyamide
- metal substituted
- 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
Landscapes
- Laminated Bodies (AREA)
Abstract
This invention relates to a preparation method of an organic-inorganic composite film which is self-mounted from transitional metal substituted polyoxometallate and Polyamide (PI)-amine tree-form molecule and is provided with electrocatalysis activity. The technical proposal is: a glassy carbon electrode or conductive glass substrate is cleaned and then go through cationization to obtain a ready-for-use substrate filmed by the glassy carbon electrode or the conductive glass substrate; the ready-for-use substrate is alternatively immerged into the transitional metal substituted polyoxometallate solution and PAMAM tree-form molecule for circulating scanning, so as to complete the self mounting of the film. By repeating the above steps, the organic-inorganic composite film with different layer numbers can be prepared. The composite film prepared by the method of the invention has the advantages of simple operation, short filming time and good uniformity, and the composite film reserves various electrochemical properties of TMPS. In particular, by using the PAMAM tree form molecule as the organic cation, the composite film is provided with high stability and high permeability. The composite film is expected to be applied to chemically modified electrodes and environmental catalysis.
Description
Technical field
The present invention relates to a kind of preparation of organic, inorganic composite film, relate to the preparation of the organic, inorganic composite film with electro catalytic activity of a kind of Transition metal substituted polyoxometallate and the self-assembly of polyamide-amide dendrimer specifically.
Background technology
Modern science and technology are the development of information technology, electronic technology, photon technology and vlsi technology particularly, the structure that drives device develops towards the direction of miniaturization, integrated, multifunction and high reliability, and the intellectuality and the filming of material proposed more and more higher requirement.Organic, inorganic composite film carries out combination with organism and inorganics on molecular level, make the existing organic flexible characteristic of material have the rigid nature of inorganics again.At present, organic, inorganic composite film is because character such as its distinctive light, electricity, magnetic, nonlinear optics have caused investigators' extensive concern.Transition metal substituted polyoxometallate (TMSP) because its particular structure, regulatable redox potential, electrode surface continuously, reversible single electron and bielectron response characteristic, extensively approved in the importance of chemically modified electrode aspect preparing in recent years.Dendrimer (dendrimer) is a class new function polymer of external in recent years exploitation, its molecular structure have height geometrical symmetry, exist a large amount of functional groups, molecular memory to increase characteristics such as having controllability at cavity, molecular chain.Polyamide-amide (PAMAM) is one of more dendrimer of research at present, it has high functionality, class spherical symmetric three-dimensional structure and constructional features such as chain entanglement do not take place for intermolecular and intramolecularly, therefore its viscosity is low, active high, chemical stability is good, and have controllable surface group, can be used as good film forming material.Self-assembly method is a kind of effective ways of constructing organic, inorganic composite film layer by layer.At present, utilize self-assembly method layer by layer, with TMSP is inorganic anion, simple chain organism is a positively charged ion, prepared some TMSP-organic self-assembled supermolecular film, but the function film that comprises Transition metal substituted polyoxometallate and near-spherical molecule-polyamide-amide yet there are no report.
Summary of the invention
The objective of the invention is to prepare the organic, inorganic composite film of Transition metal substituted polyoxometallate and polyamide-amide.Laminated film of the present invention has kept the abundant chemical property of Transition metal substituted polyoxometallate, has good stability and reusable again.
The present invention is achieved by the following technical solutions, method is as follows: at first, glass-carbon electrode substrate or conductive glass substrate are carried out substrate clean, then glass-carbon electrode substrate or conductive glass substrate are carried out cationization and obtain film forming stand-by substrate of glass-carbon electrode or the film forming stand-by substrate of conductive glass; Stand-by substrate through cationization alternately is immersed in the solution of Transition metal substituted polyoxometallic acid salts solution and pamam dendrimer molecule, and the film self-assembly is finished in scan round under certain potentials; Repeat above-mentioned scan round step, can make the organic, inorganic composite film of the different numbers of plies.
Concrete preparation process is as follows:
1, cleans
The glass-carbon electrode substrate is used successively the α-Al of 1.0,0.3 and 0.05 μ m particle diameter
2O
3Powder polishes, and then carries out ultrasonic cleaning 3～10min respectively in ethanol and distilled water, at last at 0.5molL
-1H
2SO
4CONTROLLED POTENTIAL scope-0.3～0.9V carries out cycle potentials scanning in the solution, up to obtaining stable standard rating cycle voltammogram, promptly obtains through cleaning and pretreated glassy carbon electrode substrate stand-by.
The conductive glass substrate is immersed ultrasonic cleaning 5～10min in the acetone soln, take out and use distilled water flushing; Immerse ultrasonic cleaning 2～10min in the NaOH solution again, take out and use distilled water flushing, nitrogen dries up, and promptly obtains through the conductive glass substrate that cleans stand-by.
2, cationization
To place 3～9mmolL through the glass-carbon electrode substrate that cleans
-1To soaking 12～20 hours in the amino thiophenol ethanolic soln, taking out the back cleans with distilled water, nitrogen dries up, maybe will immerse 0.7～1.2% (w through the conductive glass substrate that cleans, mass fraction) 30～50min in the PDDA solution, use deionized water rinsing again, and dry up, obtain the glass-carbon electrode substrate or the conductive glass substrate of cationization with nitrogen.
3, film self-assembly
Glass-carbon electrode substrate or conductive glass substrate through cationization place 3～9mmolL
-1In the polyoxometallic acid salts solution of Transition metal substituted, in current potential-0.3～0.9V scope with 50～100mVs
-1In sweep velocity 20～50 weeks of scanning, be placed on 0.1molL with ethanolic soln and washed with de-ionized water
-1HCl is in the solution of 0.7～1.2% (w) pamam dendrimer molecule of solvent, in current potential-0.3～0.9V scope with 50～100mVs
-1Sweep velocity 20～50 weeks of scanning; Repeat above-mentioned two processes 2～5 times, can make the organic, inorganic composite film of the required different numbers of plies.
NaOH solution of the present invention is to be that 1: 1 distilled water and alcoholic acid mixed solution is solvent prepared NaOH solution with volume ratio.
The polyoxometallic acid salts solution of Transition metal substituted of the present invention is meant with volume ratio to be 1: 1 0.5molL
-1H
2SO
4With the mixed solution of acetonitrile be the solution of the Transition metal substituted polyoxometallate of solvent preparation.
Transition metal substituted polyoxometallate molecular formula of the present invention is Na
5[P (H
2O) Mo
11XO
39], X=Cu wherein, Co, Ni, Zn or Mn are called for short PMo
11X.
Dendrimer of the present invention is 4 generations to hold amino polyamide-amide, abbreviates G4-PAMAM as, and its structural formula is as follows:
The organic, inorganic composite film of method used in the present invention and preparation is a synthetic first.Use this method to prepare organic, inorganic composite film, simple to operate, film formation time is short, the good uniformity of film, laminated film has kept the abundant chemical property of TMSP, especially use the polyamide-amide dendrimer as organic cation, thereby make laminated film have high stability and hypertonicity.This laminated film is expected to be applied aspect chemically modified electrode and the environmental catalysis.
Embodiment
Embodiment 1
1, clean:
The conductive glass substrate is immersed ultrasonic cleaning 5min in the acetone soln, take out and use distilled water flushing, immerse ultrasonic cleaning 5min in the NaOH solution, take out and use distilled water flushing, nitrogen dries up, and promptly gets through the conductive glass substrate that cleans stand-by.
2, cationization:
To immerse 30min in 1% (w, mass fraction) PDDA solution through the conductive glass substrate that cleans, and use deionized water rinsing again, nitrogen dries up, and obtains the conductive glass substrate of cationization.
3, film self-assembly:
Conductive glass substrate through cationization places 5mmolL
-1PMo
11In the solution of Cu, in-0.1～0.65V potential range with 100mVs
-1Sweep velocity scanned for 25 weeks, the back be placed in 1% (w) PAMAM solution with 100mVs with ethanolic soln and washed with de-ionized water
-1Sweep 25 weeks of speed scanning.Repeat above-mentioned two processes 3 times, can make 3 layers of organic, inorganic composite film.
The organic, inorganic composite film of preparation characterizes through the x-ray photoelectron power spectrum, has occurred the fignal center of Mo 3d and N 1s among the result, belongs to PMo respectively
11Cu and PAMAM illustrate PMo
11Cu and PAMAM have deposited in the laminated film.The fignal center of Mo 3d and N 1s strengthens along with the increase of the laminated film number of plies, illustrates that laminated film successively increases.
The atomic force microscope characterization result explanation organic, inorganic composite film surface particles of the organic, inorganic composite film of preparation is remarkable and relatively more even, shows that laminated film prepares successfully.
Embodiment 2
1, clean:
The glass-carbon electrode substrate is used successively α-Al of 1.0,0.3 and 0.05 μ m
2O
3The powder polishing, ultrasonic cleaning 10min in ethanolic soln and distilled water is at 0.5molL
-1H
2SO
4CONTROLLED POTENTIAL scope-0.1～0.65V carries out cycle potentials scanning in the solution, up to obtaining stable standard rating cycle voltammogram.
2, cationization:
To place 5mmolL through the glass-carbon electrode substrate that cleans
-1To soaking in the amino thiophenol ethanolic soln 15 hours, take out the back and clean, and dry up with nitrogen with distilled water, obtain the glass-carbon electrode substrate of cationization.
3, film self-assembly:
Glass-carbon electrode substrate through cationization places 5mmolL
-1PMo
11In the solution of Cu, in current potential-0.1～0.65V scope with 100mVs
-1Sweep speed 25 weeks of scanning, be placed in 1% (w) PAMAM solution with 100mVs with ethanolic soln and washed with de-ionized water
-1Sweep 25 weeks of speed scanning.Repeat above-mentioned two processes 5 times, can make 5 layers of organic, inorganic composite film and laminated film modified electrode.
The cyclic voltammetric behavior of the prepared laminated film of present embodiment is gone up test at CHI660 type electrochemical workstation (Shanghai occasion China instrument company).Redox peak corresponding to three 2 electronic processes of Mo has appearred in the organic, inorganic composite film that the cyclic voltammetric test result shows preparation in the potential range of-0.1-0.65V, show the PMo in the multilayer film
11Cu has kept its electrochemical properties in solution, and peak current increases along with the increase of the number of plies, and linear, shows that organic, inorganic composite film successfully prepares and has a good homogeneous.
Embodiment 3
Concrete preparation method is with reference to the preparation process of multi-layer compound film among the embodiment 1, and the x-ray photoelectron power spectrum of film and atomic force microscope characterization result show that this method has successfully prepared PMo
11The Cu/PAMAM multi-layer compound film is compared with traditional infusion method, and preparation process is simple, and required time is short, and the uniformity of film of preparation is better.
The cyclic voltammetric performance testing result of different number of plies films shows the PMo that adopts method preparation among the embodiment 2
11It is better that Cu/PAMAM laminated film and traditional infusion method are compared homogeneity, and the degree of order is higher, and circulation ratio is better.
With reference to the laminated film of embodiment 1 and embodiment 2 methods preparation in-0.1-0.65V potential range, 0.5molL
-1H
2SO
4In, with scanning speed 0.1Vs
-1Scan 50 times, peak current only has 2.7% loss, places after 1 week and at 0.5molL in air
-1H
2SO
4Solution in, current potential expands to+1.5V, scanning 20 the circle, the skeleton peak of Mo is almost constant.Even soak 1h in the phosphate buffer solution of pH=7.0, laminated film still keeps good peak shape, illustrates that the film of preparation has extraordinary stability.
Embodiment 4
Concrete preparation method is with reference to the preparation process of organic, inorganic composite film among the embodiment 2, and the electrocatalysis characteristic test is carried out on CHI660 type electrochemical workstation (Shanghai occasion China instrument company).Glass-carbon electrode (3mm) is a working electrode, and platinum wire electrode is a counter electrode, Ag/AgCl/KCl (3molL
-1) be reference electrode.Supporting electrolyte is 0.5molL
-1H
2SO
4Electrochemical method adopts cyclic voltammetry.
The modification step of glass-carbon electrode is with reference to embodiment 2.
The electrocatalysis experiment: the electrode that adopts laminated film to modify carries out the cyclic voltammetric performance test in nitrite, bromate, hydrogen peroxide and the ascorbic acid solution of different concns.Detailed process is: compound concentration is 1,2,3,4,5,7.5mmolL
-1Nitrite, bromate, superoxol and concentration be 5,10,15,20mmolL
-1Ascorbic acid solution, the electrode that organic, inorganic composite film is film modified places above-mentioned solution, in-0.15-0.65V potential range, with 20mVL
-1Scanning speed, carry out cyclic voltammetry scan.
Electro catalytic activity is estimated: NO
2 -, BrO
3 -And H
2O
2Oxidizing reaction on naked glass-carbon electrode is difficult to carry out because bigger overpotential is arranged in reduction reaction on the naked glass-carbon electrode and xitix.Compare with bare electrode, the laminated film modified electrode presents good electro catalytic activity to above-mentioned 4 kinds of material tools.Along with NO
2 -, BrO
3 -And H
2O
2The increase of concentration, the second, the three reduction peak current of Mo increases gradually, and Dui Ying oxidation peak current reduces with it, and that first redox peak of Mo changes is very little, shows that 4 electron reductions of Mo and 6 electron reduction things are to NO
2 -, BrO
3 -And H
2O
2Has katalysis.For the catalyzed oxidation of xitix, along with the increase of ascorbic acid concentrations, anodic peak current significantly increases, and cathodic peak current reduces.Catalytic wave appears at PMo
11First oxidation wave place of Cu is corresponding to PMo
112 electronics of Cu are to the oxidation of 0 electronics, and the adding of xitix is to peak II, and III is not influence almost.By changing the number of plies of multilayer film, can regulate PMo
11The content of Cu in multilayer film, thus its catalytic activity regulated.
Embodiment 5
1, clean:
Conductive glass is immersed ultrasonic cleaning 5min in the acetone soln, take out and use distilled water flushing, immerse ultrasonic cleaning 6min in the NaOH solution, take out and use distilled water flushing, nitrogen dries up, and promptly gets the conductive glass substrate through cleaning.
2, cationization:
To immerse 40min in the 0.7%PDDA solution through the conductive glass that cleans, and use deionized water rinsing again, nitrogen dries up, and obtains the conductive glass substrate of cationization.
3, film self-assembly:
Conductive glass substrate through cationization places 3mmolL
-1PMo
11In the solution of Co, in-0.15～0.7V potential range with 50mVs
-1Sweep velocity scanned for 30 weeks, and the back is placed in 0.7% (w) PAMAM solution in-0.15～0.7V potential range with 50mVs with ethanolic soln and washed with de-ionized water
-1Sweep velocity scanned for 30 weeks, repeated above-mentioned two processes, can make 5 layers of required organic, inorganic composite film.
The laminated film of preparation characterizes through the x-ray photoelectron power spectrum, has occurred the fignal center of Mo 3d and N 1s among the result, belongs to PMo respectively
11Co and PAMAM illustrate PMo
11Co and PAMAM have deposited in the laminated film.The fignal center of Mo 3d and N 1s strengthens along with the increase of the laminated film number of plies, illustrates that laminated film successively increases.
The atomic force microscope characterization result explanation laminated film surface particles of laminated film is remarkable and relatively more even, shows that laminated film prepares successfully.
Embodiment 6
1, clean:
The glass-carbon electrode substrate is used successively α-Al of 1.0,0.3 and 0.05 μ m
2O
3The powder polishing, ultrasonic cleaning 10min in ethanolic soln and distilled water is at 0.5molL
-1H
2SO
4CONTROLLED POTENTIAL scope-0.15～0.7V carries out cycle potentials scanning in the solution, up to obtaining stable standard rating cycle voltammogram.
2, cationization:
To place 3mmolL through the glass-carbon electrode that cleans
-1To soaking in the amino thiophenol ethanolic soln 18 hours, take out the back and clean, and dry up with nitrogen with distilled water, obtain the glass-carbon electrode substrate of cationization.
3, film self-assembly:
Glass-carbon electrode substrate through cationization places 3mmolL
-1PMo
11In the solution of Co, in-0.15～0.7V potential range with 50mVs
-1Sweep speed 30 weeks of scanning, be placed in 0.7% (w) PAMAM solution, repeat above-mentioned scanning process, can make required 6 layers of organic, inorganic composite film and film modified electrode with ethanolic soln and washed with de-ionized water.
The cyclic voltammetric behavior of laminated film is gone up test at CHI660 type electrochemical workstation (Shanghai occasion China instrument company).Redox peak corresponding to three 2 electronic processes of Mo has appearred in the laminated film that the cyclic voltammetric test result shows preparation in the potential range of-0.15-0.7V, show the PMo in the multilayer film
11Co has kept its electrochemical properties in solution, and peak current increases along with the increase of the number of plies, and linear, shows that laminated film successfully prepares and has a good homogeneous.
Embodiment 7
Concrete preparation method is with reference to the preparation process of laminated film among the embodiment 5, and the x-ray photoelectron power spectrum of film and atomic force microscope characterization result show that this method has successfully prepared PMo
11The Co/PAMAM organic, inorganic composite film is compared with traditional infusion method, and preparation process is simple, and required time is short, and the uniformity of film of preparation is better.
The cyclic voltammetric performance testing result of laminated film shows the PMo that adopts method preparation among the embodiment 5
11It is better that Co/PAMAM organic, inorganic composite film and traditional infusion method are compared homogeneity, and the degree of order is higher, and circulation ratio is better.
The organic, inorganic composite film of this method preparation placed for 2 week in air after, the skeleton peak of Mo is almost constant.In-0.15-0.7V potential range, 0.5molL
-1H
2SO
4In, with 0.1Vs
-1Scanning speed scanned for 100 weeks, and peak current only has 6.7% loss, even soak 1.5h in the phosphate buffer solution of pH=7.0, multilayer film still keeps good peak shape, illustrated that the organic and inorganic film of preparation has good stability.
Embodiment 8
Concrete preparation method is with reference to the preparation process of multilayer organic, inorganic composite film among the embodiment 6, and electrocatalysis characteristic is tested with reference to the electrocatalysis characteristic testing method among the embodiment 4.
The modification step of glass-carbon electrode is with reference to embodiment 6.
The electrocatalysis experiment: the electrode of modifying by laminated film carries out the cyclic voltammetric performance test in nitrite, bromate, hydrogen peroxide and the ascorbic acid solution of different concns.Detailed process is: compound concentration is 2,4,6,8,10,15mmolL
-1Nitrite, bromate, the solution and the concentration of hydrogen peroxide be 5,10,15,20mmolL
-1Ascorbic acid solution, the electrode that laminated film is modified places above-mentioned solution, in-0.15-0.7V potential range, with 20mVL
-1Scanning speed carry out cyclic voltammetry scan.
Electro catalytic activity is estimated: NO
2 -, BrO
3 -And H
2O
2Oxidizing reaction on naked glass-carbon electrode is difficult to carry out because bigger overpotential is arranged in reduction reaction on the naked glass-carbon electrode and xitix.Compare with bare electrode, the above-mentioned 4 kinds of materials of electrode pair that laminated film is modified present good electro catalytic activity.Along with NO
2 -, BrO
3 -And H
2O
2The increase of concentration, the 3rd reduction peak current of Mo increases gradually, and Dui Ying oxidation peak current reduces with it, and preceding two redox peaks variation of Mo is very little, the 6 electron reduction things that show Mo are to NO
2 -, BrO
3 -And H
2O
2Has katalysis.For the catalyzed oxidation of xitix, along with the increase of ascorbic acid concentrations, anodic peak current significantly increases, and cathodic peak current reduces.Catalytic wave appears at PMo
11First oxidation wave place of Co is corresponding to PMo
112 electronics of Co are to the oxidation of 0 electronics, and the adding of xitix is to peak II, and III is not influence almost.By changing the number of plies of laminated film, can regulate PMo
11The content of Co in laminated film.
Because the Transition metal substituted polyoxometallate enriches the high functionality and the hypertonicity of adjustable electrochemical properties and polycation daiamid, make organic, inorganic composite film have good stability and catalytic activity by the electrostatic interaction preparation, and can reuse, the present invention reaches containing nitrite at the waste water that improvement contains above-mentioned substance, has a wide range of applications in the food inspection of xitix.
Claims (9)
1, a kind of Transition metal substituted polyoxometallate and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that:
At first glass-carbon electrode substrate or conductive glass substrate are cleaned, then glass-carbon electrode substrate or conductive glass substrate are carried out cationization and obtain film forming stand-by substrate of glass-carbon electrode or the film forming stand-by substrate of conductive glass;
Stand-by substrate through cationization alternately is immersed in the solution of Transition metal substituted polyoxometallic acid salts solution and polyamide-amide dendrimer, and the film self-assembly is finished in scan round under certain potentials;
The recirculation scanning step can make the organic, inorganic composite film of the different numbers of plies.
2, Transition metal substituted polyoxometallate according to claim 1 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that the described glass-carbon electrode substrate is cleaned is meant the α-Al that the glass-carbon electrode substrate is used successively 1.0,0.3 and 0.05 μ m particle diameter
2O
3The powder polishing is then carried out ultrasonic cleaning 3～10min with ethanolic soln and distilled water respectively again, is 0.5molL in concentration at last
-1H
2SO
4Carry out cycle potentials scanning in the solution, obtain through cleaning and the pretreated glassy carbon electrode substrate; Or conductive glass immersed ultrasonic cleaning 5～10min in the acetone soln, and immerse ultrasonic cleaning 2～10min in the NaOH solution behind the distilled water flushing again, flushing, nitrogen dries up, and obtains the conductive glass substrate through cleaning.
3, Transition metal substituted polyoxometallate according to claim 2 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that described NaOH solution is is that distilled water and the alcoholic acid mixed solution of 1:1 is solvent prepared NaOH solution with the volume ratio.
4, Transition metal substituted polyoxometallate according to claim 1 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that described glass-carbon electrode substrate cationization is meant process to be cleaned and the pretreated glassy carbon electrode substrate places 3～9mmolL
-1To soaking 12～20 hours in the amino thiophenol ethanolic soln, take out the back and clean with distilled water, nitrogen dries up, and obtains the glass-carbon electrode substrate of cationization.
5, Transition metal substituted polyoxometallate according to claim 1 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that described conductive glass substrate cationization is meant that will pass through the conductive glass substrate that cleans immerses 30～50min in 0.7～1.2%PDDA solution, use deionized water rinsing again, and dry up with nitrogen, obtain the conductive glass substrate of cationization.
6, Transition metal substituted polyoxometallate according to claim 1 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that described film self-assembly is meant glass-carbon electrode substrate or conductive glass substrate through cationization, places 3～9mmolL
-1In the solution of the polyoxometallate of Transition metal substituted, in current potential-0.3～0.9V scope with 50～100mVs
-1In sweep velocity 20～50 weeks of scanning, be placed on 0.1molL with ethanolic soln and washed with de-ionized water
-1HCl is in the solution of 0.7～1.2% (w) pamam dendrimer molecule of solvent, in current potential-0.3～0.9V scope with 50～100mVs
-1In sweep velocity 20～50 weeks of scanning, repeat above-mentioned two processes 2～5 times.
7, Transition metal substituted polyoxometallate according to claim 6 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that the polyoxometallic acid salts solution of described Transition metal substituted is meant with the volume ratio to be the 0.5molL of 1:1
-1H
2SO
4With the mixed solution of acetonitrile be the solution of the Transition metal substituted polyoxometallate of solvent preparation.
8, Transition metal substituted polyoxometallate according to claim 6 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, and the molecular formula that it is characterized in that described Transition metal substituted polyoxometallate is Na
5[P (H
2O) Mo
11XO
39], wherein X=Cu, Co, Ni, Zn or Mn.
9, Transition metal substituted polyoxometallate according to claim 6 and polyamide-amide self-assembly prepare the method for organic, inorganic composite film, it is characterized in that described dendrimer is 4 generations to hold amino polyamide-amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100716425A CN101386471B (en) | 2008-08-27 | 2008-08-27 | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100716425A CN101386471B (en) | 2008-08-27 | 2008-08-27 | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101386471A true CN101386471A (en) | 2009-03-18 |
| CN101386471B CN101386471B (en) | 2011-03-30 |
Family
ID=40476176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100716425A Expired - Fee Related CN101386471B (en) | 2008-08-27 | 2008-08-27 | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101386471B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099183A (en) * | 2017-03-31 | 2017-08-29 | 廊坊立邦涂料有限公司 | A kind of thickener composition for water-soluble high-molecular compound and the aqueous coating composition containing said composition |
| CN108014820A (en) * | 2017-12-01 | 2018-05-11 | 济南大学 | A kind of molybdenum disulfide elctro-catalyst with nanometer multilayer membrane structure and preparation method thereof |
| CN111530499A (en) * | 2020-05-15 | 2020-08-14 | 中自环保科技股份有限公司 | Synthesis method of core-shell alloy electrocatalyst with controllable structure |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074447A2 (en) * | 2001-03-21 | 2002-09-26 | Nippon Sheet Glass Co., Ltd. | Coated article, coating liquid composition, and method for producing coated article |
| CN1903561A (en) * | 2005-07-27 | 2007-01-31 | 中国科学院福建物质结构研究所 | Self-assembling organic-inorganic composite film made of various kinds of metal oxy-acidic salts and thia-calicene aromatic hydrocarbon |
-
2008
- 2008-08-27 CN CN2008100716425A patent/CN101386471B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099183A (en) * | 2017-03-31 | 2017-08-29 | 廊坊立邦涂料有限公司 | A kind of thickener composition for water-soluble high-molecular compound and the aqueous coating composition containing said composition |
| CN108014820A (en) * | 2017-12-01 | 2018-05-11 | 济南大学 | A kind of molybdenum disulfide elctro-catalyst with nanometer multilayer membrane structure and preparation method thereof |
| CN108014820B (en) * | 2017-12-01 | 2020-07-17 | 济南大学 | Molybdenum disulfide electrocatalyst with nano multilayer film structure and preparation method thereof |
| CN111530499A (en) * | 2020-05-15 | 2020-08-14 | 中自环保科技股份有限公司 | Synthesis method of core-shell alloy electrocatalyst with controllable structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101386471B (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | Comparison of oxygen reduction reaction at silver nanoparticles and polycrystalline silver electrodes in alkaline solution | |
| Sun et al. | A novel layer-by-layer self-assembled carbon nanotube-based anode: Preparation, characterization, and application in microbial fuel cell | |
| CN108682561A (en) | A kind of electrode material for super capacitor and preparation method | |
| Li et al. | Immobilization of a molecular catalyst on carbon nanotubes for highly efficient electro-catalytic water oxidation | |
| CN105869916B (en) | A kind of preparation method of hydroxy cobalt oxide nanotube electrode | |
| CN108130552A (en) | A kind of polyaniline cuprous oxide composite material and its preparation method and application | |
| Raoof et al. | A novel, effective and low cost catalyst for methanol oxidation based on nickel ions dispersed onto poly (o-toluidine)/Triton X-100 film at the surface of multi-walled carbon nanotube paste electrode | |
| CN110223847A (en) | A kind of electrode material for super capacitor and preparation method | |
| CN101386471B (en) | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine | |
| CN108070826B (en) | A method of preparing gold electrode surfaces dopamine self-assembled monolayer | |
| JP4553732B2 (en) | Method for producing electrode for electrochemical device | |
| CN112164592A (en) | CeO (CeO)2Nanoparticle modified Co3S4Preparation method of nanosheet array | |
| Liu et al. | Potential stability improvement in Pb2+ ion selective electrodes by applying hydrophobic polyaniline as ion-to-electron transducer | |
| CN108033492B (en) | The CoWO of amorphous4The preparation method of cage-shaped nano material and its application in electro-catalysis | |
| JP5109323B2 (en) | Electrode for electrochemical device, method for producing the same, and electrochemical device | |
| KR101869646B1 (en) | Manufacturing method of catalyst for reducing carbon dioxide and oxydizing formic acid, catalyst for reducing carbon dioxide and oxydizing formic acid manufactured by the same | |
| CN104928713A (en) | Preparation method and application of nickel-based hydrogen production electrode coated with conducting polymers | |
| Natarajan et al. | Ultrasonication-assisted synthesis of nickel tungstate decorated on polydimethoxyaniline nanocomposite catalyst for potential direct methanol fuel cell application | |
| Fotouhi et al. | ZnO/Polytyramine nanocomposite film: Facile electrosynthesis and high performance electrocatalytic activity toward methanol oxidation | |
| CN113380554B (en) | VO with nanorod structure x @MoPO 4 Electrode material and preparation method and application thereof | |
| CN109453808A (en) | A kind of graphene/Pt/Polypyrrole composite material preparation method and applications of three-dimensional multistage hole | |
| Hu et al. | Flexible composite Ag-AgNWs-CF as low noise marine electric field sensor | |
| CN101487124A (en) | Method for forming arginine self-assembly corrosion inhibition film on copper surface | |
| CN101714636A (en) | Composite thin film anode catalyst of direct methanol fuel cell and preparation method thereof | |
| Ojani et al. | High electrocatalysis of ethylene glycol oxidation based on nickel particles electrodeposited into poly (m-toluidine)/Triton X-100 composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110330 Termination date: 20130827 |