CN1903561A - Self-assembling organic-inorganic composite film made of various kinds of metal oxy-acidic salts and thia-calicene aromatic hydrocarbon - Google Patents
Self-assembling organic-inorganic composite film made of various kinds of metal oxy-acidic salts and thia-calicene aromatic hydrocarbon Download PDFInfo
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- CN1903561A CN1903561A CN 200510088319 CN200510088319A CN1903561A CN 1903561 A CN1903561 A CN 1903561A CN 200510088319 CN200510088319 CN 200510088319 CN 200510088319 A CN200510088319 A CN 200510088319A CN 1903561 A CN1903561 A CN 1903561A
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Abstract
An organic-inorganic composite film is prepared from XW12, where X=B, Si and P, or M4(H2O)2(PW9O34)2, where M=Co, Cu, Zn and Mn, and p-tetraamino-tetrathiacalix [4] arene through layer-layer self-assembling. It has high electrochemical properties.
Description
Technical field
The present invention relates to a kind of organic, inorganic composite film, relate in particular to the organic and inorganic film of a kind of polyoxometallate and the self assembly of amination Thiacalixarene.
Background technology
Along with the develop rapidly of electronics and information science, people have proposed more and more higher requirement to material, require the microminiaturization, multifunction, integrated etc. of device.Yet single species is formed the material of preparation and is difficult to satisfy simultaneously multiple needs.And the organic and inorganic composite membrane carries out combination with organic matter and inorganic matter on molecular level, makes material promptly have the performance that organic feature has inorganic matter again.Polyoxometallate (Polyoxometalates, POMs), inorganic metal oxygen cluster compound as a quasi-representative has abundant structures, chemistry and performance physically, thereby it has important theoretical research value and wide application prospect in fields such as catalysis, medicine and materials chemistries.Calixarenes is subjected to scientific worker's extensive attention as the novel macrocyclic compound with unique void structure of a class in the achievement that obtains aspect the supramolecular chemistry research.Calixarenes has application potential widely in fields such as liquid film transmission, complexometric extraction, molecular probe, molecular device, sensor, liquid crystal, nonlinear opticses.Thiacalixarene is a class cyclic oligomer that is formed by connecting at the phenolic hydroxyl group ortho position by sulfur heteroatom by phenol units, and Thiacalixarene has some unique new properties owing to have sulfide group.Yet the preparation of their these its films of potentiality application need.Self-assembly method is a kind of effective ways of constructing the organic and inorganic composite membrane layer by layer.At present, utilize self-assembly method layer by layer, as inorganic anion, simple chain organic matter is a cation, has prepared the organic self-assembled supermolecular film of a series of POMs-with POMs.But the organic cation of report use at present is some simple chain organic cations, yet there are no report and contain the macrocyclic compound Thiacalixarene as organic cation.
Summary of the invention
The objective of the invention is to prepare the organic and inorganic composite membrane of a kind of polyoxometallate and amination thia cup [4] aromatic hydrocarbons.This composite membrane promptly has the abundant chemical property of polyoxometallate, has the characteristics of calixarenes macrocyclic compound again, is a kind of compound film with multifunction.
The present invention is achieved by the following technical solutions, and method is as follows: at first, quartz glass plate or glass-carbon electrode are carried out cleaning treatment, clean with distilled water, nitrogen dries up; Quartz glass plate after will handling then or glass-carbon electrode are immersed in cationization in polymine (PEI) solution; Again 20min in solution that alternately is immersed in polyoxometallate (POMs) through the substrate of cationization and the amination Thiacalixarene solution, each immerses and cleans with distilled water after step is taken out, nitrogen dries up, and this step that circulates can make the organic and inorganic composite membrane of the different numbers of plies.
The polyoxometallate that the present invention adopts is XW
12(X=B, Si, P) or [M of Transition metal substituted
4 II(H
2O)
2(PW
9O
34)
2]
10-(M=Co, Cu, Zn, Mn).
The amination Thiacalixarene that the present invention adopts be (p-tetraamino-tetrathiacalix[4] arene), abbreviation pATC4, and its structural formula is as follows.
The organic and inorganic composite membrane of the present invention's preparation is synthetic first.This composite membrane promptly has the abundant chemical property of polyoxometallate, has the characteristics of calixarenes macrocyclic compound again, is a kind of compound film with multifunction; Especially use amination thia cup [4] aromatic hydrocarbons as organic cation, this composite membrane is expected to be applied on chemically modified electrode and sensor.
The specific embodiment
Embodiment 1:(BW
12/ pATC4)
nThe preparation of multilayer organic and inorganic film
At first, quartz plate is cleaned: quartz glass plate is placed 98%H
2SO
4With 30%H
2O
2(7: in 80 ℃ of following impregnation process 40min, take out the back and clean in mixed liquor 3v/v) with distilled water; Immerse H again
2O: H
2O
2: NH
3=5: in 80 ℃ of following impregnation process 20min, take out the back and clean with distilled water in the mixed liquor of 1: 1 (v/v/v), nitrogen dries up, and promptly obtains the stand-by substrate of film forming.
Again substrate is carried out the PEI cationization: will immerse in the polymine PEI solution of 10mg/mL through the substrate of aforementioned processing program and place 20min, and take out the back and clean with distilled water, nitrogen dries up.
And then, alternately immerse 4.0 * 10 substrate through the PEI cationization
-2The BW of M
12Solution and 2.0 * 10
-3In the M pATC4 solution (through the persalt cationization), place 20min respectively, each immerses and cleans with distilled water after step is taken out, and nitrogen dries up; The above step of repetitive cycling can make required (BW
12/ pATC4)
nMultilayer organic and inorganic film.
The uv-vis spectra of film is characterized in the ultraviolet-visual spectrometer of the Lambda-35 type of U.S. PerkinElmer company production.Uv-vis spectra shows that the film of preparation is at wavelength 260nm and the BW of 325nm place
12The increase that the absorbance of/pATC4 is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.
Embodiment 2:([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ pATC4)
nThe preparation synthesis step of multilayer organic and inorganic film and testing procedure are with reference to embodiment 1.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10
-3[the Co of M
4 II(H
2O)
2(PW
9O
34)
2]
10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 250nm and the [Co of 325nm place
4 II(H
2O)
2(PW
9O
34)
2]
10-The increase that the absorbance of/pATC4 is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.
Embodiment 3:(BW
12/ pATC4)
nThe electrochemical behavior of multilayer organic and inorganic film characterizes
Electrochemical behavior adopts the electrochemical workstation of the Epsilon type of U.S. BAS company production to carry out.Glass-carbon electrode (3mm) is a working electrode, and platinum electrode is to electrode, and Ag/AgCl/KCl (3M) is a reference electrode.Supporting electrolyte is a 0.1M NaCl solution.Electrochemical method adopts cyclic voltammetry.
The working electrode modification step is as follows: at first, (diameter 3mm) carries out preliminary treatment to glass-carbon electrode, uses 1.0,0.3 and 0.05 μ m α-Al continuously
2The O3 polishing powder polishes respectively, each polishing back acetone and distilled water ultrasonic cleaning, last nitrogen drying; Immerse in the polymine PEI solution of 10mg/mL again and place 20min, take out the back and clean with distilled water, nitrogen dries up; And then, alternately immerse 4.0 * 10 glass-carbon electrode through the PEI cationization
-2The BW of M
12Solution and 2.0 * 10
-3In the MpATC4 solution (through the persalt cationization), place 20min respectively, each immerses and cleans with distilled water after step is taken out, and nitrogen dries up; Can make required (BW
12/ pATC4) the complex film modified glass-carbon electrode of organic and inorganic.
Film (BW
12/ pATC4) electrochemical behavior of modified glassy carbon shows that negative voltage belt has two pairs of continuous redox peaks, comes from BW
12, its oxidation-reduction potential is respectively-0.631mV and-0.386mV; And a pair of redox peak appears at positive voltage belt, and coming from pATC4, its oxidation-reduction potential is+0.075mV.The polyoxometallate BW in the film wherein
12Performance is to H
2O
2Certain electrocatalysis (supporting electrolyte is that cushioning liquid liquid acetic acid and sodium acetate pH are 5.8) is arranged.
Film (BW
12/ pATC4) modified glassy carbon is immersed in 10mM CuCl
2Or RuCl
320min in the solution takes out the back and cleans with distilled water, and nitrogen dries up, and tests its chemical property again.Cyclic voltammetry shows pATC4 redox peak generation significant change, becomes irreversible.Because pATC4 is the macrocyclic compound with phenolic hydroxyl group void structure, the pATC4 performance in the film is to Cu
2+, Ru
3+Deng transition metal ions weak coordination takes place, thereby the film of preparation is expected to be applied aspect metal ion sensor.
Embodiment 4:([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ pATC4) electrochemical behavior of organic and inorganic composite membrane characterizes
Characterize step with reference to embodiment 3, but the solution that the glass-carbon electrode of PEI cationization alternately immerses adopts 5.0 * 10
-3[the Co of M
4 II(H
2O)
2(PW
9O
34)
2]
10-Solution, supporting electrolyte are that cushioning liquid liquid acetic acid and sodium acetate pH are 4.4.
([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ pATC4)
nThe electrochemical behavior of modified glassy carbon electrode shows that negative voltage belt has three pairs of continuous redox peaks, comes from [Co
4 II(H
2O)
2(PW
9O
34)
2]
10-, its oxidation-reduction potential is respectively-715mV ,-593mV and-439mV; And a pair of redox peak appears at positive voltage belt, and coming from pATC4, its oxidation-reduction potential is+428mV.[the Co in the film wherein
4 II(H
2O)
2(PW
9O
34)
2]
10-Performance is to NO
2 -Certain electrocatalysis (supporting electrolyte is that cushioning liquid liquid acetic acid and sodium acetate pH are 4.4) is arranged.
With film (Co
4 II(H
2O)
2(PW
9O
34)
2)
10-/ pATC4) modified glassy carbon is immersed in 10mMCuCl
2Or RuCl
320min in the solution takes out the back and cleans with distilled water, and nitrogen dries up, and tests its chemical property again.Cyclic voltammetry shows that pATC4 redox peak current reduces.Because pATC4 is the macrocyclic compound with phenolic hydroxyl group void structure, the pATC4 performance in the film is to Cu
2+, Ru
3+Deng transition metal ions weak coordination takes place, thereby the film of preparation is expected to be applied aspect metal ion sensor.
Claims (5)
1. the organic and inorganic film of polyoxometallate and Thiacalixarene self assembly, it is characterized in that: this film is by XW
12(X=B, Si, P) and p-tetraamino-tetrathiacalix[4] arene forms.
2. organic and inorganic film as claimed in claim 1 is characterized in that: described XW
12By [M
4 II(H
2O)
2(PW
9O
34)
2]
10-(Zn Mn) replaces for M=Co, Cu.
3. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW
12/ pATC4)
nMultilayer organic and inorganic film.
4. organic and inorganic film as claimed in claim 2 is characterized in that: this organic and inorganic film is ([Co
4 II(H
2O)
2(PW
9O
34)
2]
10-/ pATC4)
nMultilayer organic and inorganic film.
5. the preparation method of claim 1 or 2 or 3 or 4 organic and inorganic film, it is characterized in that: substrate adopts the polyethyleneimine: amine aqueous solution to carry out cationization.
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|---|---|---|---|
| CN 200510088319 CN1903561A (en) | 2005-07-27 | 2005-07-27 | Self-assembling organic-inorganic composite film made of various kinds of metal oxy-acidic salts and thia-calicene aromatic hydrocarbon |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386471B (en) * | 2008-08-27 | 2011-03-30 | 福建师范大学 | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine |
| JP2020007319A (en) * | 2019-08-14 | 2020-01-16 | 株式会社リコー | Compound, electrode material, and electrode |
| CN112619700A (en) * | 2020-12-28 | 2021-04-09 | 扬州大学 | Column [5]]Aromatic hydrocarbon-Zn2Sb2Supermolecule nanosphere catalyst and preparation method thereof |
-
2005
- 2005-07-27 CN CN 200510088319 patent/CN1903561A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386471B (en) * | 2008-08-27 | 2011-03-30 | 福建师范大学 | Self-assembly preparation of organic/inorganic compound film by transient metal substitution of polyoxometallate and polyamide-amine |
| JP2020007319A (en) * | 2019-08-14 | 2020-01-16 | 株式会社リコー | Compound, electrode material, and electrode |
| CN112619700A (en) * | 2020-12-28 | 2021-04-09 | 扬州大学 | Column [5]]Aromatic hydrocarbon-Zn2Sb2Supermolecule nanosphere catalyst and preparation method thereof |
| CN112619700B (en) * | 2020-12-28 | 2024-04-05 | 扬州大学 | Column [5]]Aromatic hydrocarbon-Zn 2 Sb 2 Supermolecule nanosphere catalyst and preparation method thereof |
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Open date: 20070131 |