CN101774627A - Method for preparing polyoxometallate micron tubular material doped by metal ions - Google Patents
Method for preparing polyoxometallate micron tubular material doped by metal ions Download PDFInfo
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- CN101774627A CN101774627A CN201010030815A CN201010030815A CN101774627A CN 101774627 A CN101774627 A CN 101774627A CN 201010030815 A CN201010030815 A CN 201010030815A CN 201010030815 A CN201010030815 A CN 201010030815A CN 101774627 A CN101774627 A CN 101774627A
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- polyoxometallate
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Abstract
The invention belongs to a chemosynthesis method and particularly relates to a method for preparing a polyoxometallate micron tubular material doped by metal ions. A Km[ZM11XO39] or a KmXn[ZM12O40] micron tube is synthesized by using template-free aqueous solution in one step, wherein X may be Li+, Mg2+, Cr3+, Mn2+ and the like, Z may be Si, Ge and the like, and M may be W, Mo and the like. Micron tubes are obtained by converting polyoxometallate of an unsaturated series into polyoxometallate of a saturated series under the condition of the appropriate pH value and temperature, and synchronizing the crystal growth of the polyoxometallate of the saturated series. In the method, the metal ions are doped into the corresponding material to improve the mobility of current carriers of the material, so that the conductivity of the material is improved and the pyroelectricity is improved; the metal ions are doped in the process of preparing catalysts, so that the stability, selectivity and catalytic activity of the catalysts are improved effectively. Thus, the preparation of the POM micron tube doped by metal ions has a great significance and a potential application prospect.
Description
Technical field
The invention belongs to chemical synthesis process, be specifically related to the preparation method of the polyoxometallate micron tubular material of metal ion mixing.
Background technology
At present, the research of carbon nanotube has obtained huge progress, and its applied research is very extensive, has contained from bio-science, information science, electric light magnetics to numerous areas such as environmental sciences.Meanwhile, the report of other inorganic Nano/micro tubulose materials increases sharply, the feasible concern that the experiment and the theoretical investigation of hollow circuit cylinder structured material are subjected to increasing scientific worker.1992, Tenne etc. successfully synthesized first inorganic nano-tube (WS
2), they have synthesized MoS again in nineteen ninety-five subsequently
2Nanotube, for inorganic nano-tube synthetic opened up new road, but these the earliest the synthetic inorganic nano-tube be the inorganic materials with two-dimensional layered structure similar mostly to graphite.Because they have the lamella similar to graphite, by selecting suitable experiment condition, the single lamella of these materials also is similar to graphite flake and is curled into nanotube.Afterwards, the nanotube of metal oxide is as TiO
2, Er
2O
3, ZnO, In
2O
3, SiO
2Deng; The nanotube of transition metal halide is as NiCl
2Metal nano-tube, as Au, Co, Fe, Cu, Ni etc. also are in the news.Meanwhile, micron tube has also attracted the great attention of scientist, and has obtained some very valuable achievements in research.For example Junqing Hu etc. utilizes metal auxiliary catalysis method to synthesize carbon micron tube; Schnur etc. utilize the self-assembly of polymerizable diacetylene base glycerol phosphatidylcholine molecules to synthesize microtubule the earliest; People such as Martin have made the conduction high polymer micron tube in liquid polymerization, and prepare the metal micron tube with electrochemical deposition of metal on membranous pore structure, or the like.Micron tube has good chemical stability, mechanical property and monodispersity, and can carry out single operation to it by means of the micron operative technique.The application of micron tube will obtain extensive and deep research.
The general name of polyoxometallic acid and salt thereof (POM) multi-metal oxygen cluster that to be a class formed by transition metal such as molybdenum, tungsten, vanadium and/or niobium and oxygen, its diversity structure and their oxidation-reduction quality, catalytic performance, antiviral performance, magnetic performance etc. make them be widely used in every field.The characteristic of POM and Nano/micro tube shape structure is incorporated into one prepares tubular material, will have certain theoretical significance and practical significance based on POM.For example people such as Enbo Wang utilizes simple PEG/H
2The O liquid-phase system has synthesized Ag
4SiW
12O
40Micron tube; People such as Bin Ding by calcining be wrapped on the electrospinning fibre thing the layer connect the layer (LBL) structure ultra-thin composite membrane prepared Keggin type polyacid (H
4SiW
12O
40) nanotube; In the recent period, Cronin has reported the micron tube that POM and organic cation generate.We have synthesized α-K by an one-step template-free aqueous solution
4SiW
12O
40Micron tube.This micron tube is converted into saturated serial polyoxometallate by unsaturated serial polyoxometallate and obtains synchronously with its crystal growth under suitable pH and temperature condition.Utilize this mechanism, can add the POM micron tubular material that other metal ions prepare metal ion mixing.In view of this consideration, we have further expanded the research of POM Nano/micro tube shape material, have prepared the POM micron tube of multiple metal ion mixing.
Summary of the invention
The objective of the invention is in order to reduce synthetic cost, and the excellent specific property that makes full use of the POM of doped metal ion provides a kind of preparation method with micron tube material of fine using value.
The polyoxometallate micron tube of metal ion mixing is in suitable pH and temperature range, adds other metal ions preparations by unsaturated serial polyoxometallate.Can control the size of caliber by changing reaction conditions.This many components doping polyoxometallate micron tubular material can be applicable to organic catalysis, electrochemical sensor, gas-liquid storer, medicament slow release, many-sides such as photoelectric functional material and magneticsubstance.
The preparation method of the POM micron tube material of doped metal ion of the present invention may further comprise the steps:
(1) with unsaturated Keggin series heteropolyacid salt with 1-6: 10 mass ratio is dissolved in the water, and the pH that regulates this stock liquid is between 0-4.
(2) place 60-90 ℃ of water-bath to heat step (1) gained solution.
(3) salt that step (2) gained solution is added metal ion mixes, as adding CoCl
2Carry out Co
2+Doping etc.
(4) cooling step (3) gained solution is to room temperature, and suction filtration can obtain the POM micron tube material (as figure) of metal ion mixing.
The general formula of the POM micron tube material of doped metal ion: Km[ZM
11XO
39] or KmXn[ZM
12O
40] (X=Li
+, Mg
2+, Cr
3+, Mn
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+Deng; Z=Si, Ge etc.; M=W, Mo etc.).
Metal ion mixing of the present invention is a kind of approach of regulating material property by the manufacturing lattice imperfection.Doped metal ion can improve material carrier mobility in corresponding material, its specific conductivity is improved, and pyroelectricity improves; In the process of some particle growth, the metal ion that mixes can be used as the pattern that the potential style control agent is regulated and control particle; Doped metal ion in catalyst preparation process can effectively improve stability, selectivity and the catalytic activity of catalyzer.Therefore, the POM micron tube of preparation doped metal ion has great importance and potential application foreground.
The effect of the POM micron tube material of doped metal ion of the present invention is as follows:
1, the POM micron tube of doped metal ion is utilized the induction of metal ion to some biological substance, and is bigger in conjunction with the micron tube specific surface area, and the comparatively responsive advantage of the change of factor can be made biosensor to this micron tube to external world.
2, the POM micron tube of doped metal ion is utilized the sequestering action of metal ion and organic fluorescence chromophoric group, prepares photoluminescence or electroluminescent material.
3, the POM micron tube of doped metal ion can utilize the wicking action of micron tube to be designed to microreactor, microstorage, and slow release device.
4, institute's synthetic micron tube, because specific surface area is bigger, just big with the contact area of reactant, and metal ion some organic reaction carry out can be used as promotor in the process, thereby assist the carrying out of reaction, improve the selectivity and the activity of catalyzed reaction.
The present invention can eliminate the constraint of severe condition such as High Temperature High Pressure or strong electron beam in the micron tube material building-up process and the restriction of template selection aspect, reduce synthetic cost, and the characteristic of excellence that makes full use of the POM of doped metal ion provides a kind of micron tube material with fine using value.
Description of drawings
Fig. 1 is the doping different metal ion Li that breaks away from mother liquor
+, Mg
2+, Cr
3+, Mn
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+, Zn
2+And Cd
2+The optical microscope photograph of POM micron tube;
Fig. 2 is doped metal ion Li
+, Fe
3+And Cd
2+The infrared spectrogram of POM micron tube;
Fig. 3 is doped metal ion Cr
3+, Co
2+And Ni
2+The ultraviolet-visible spectrogram of POM micron tube;
Fig. 4 is doped metal ion Zn
2+The POM micron tube in the x-ray photoelectron of Zn element can spectrogram;
Fig. 5 is doped metal ion Zn
2+The POM micron tube in the x-ray photoelectron of W element can spectrogram;
Fig. 6 is doped metal ion Zn
2+The POM micron tube in the x-ray photoelectron of O element can spectrogram.
Embodiment
Embodiment 1
With α-silicotungstic acid sylvite (α-K
8SiW
11O
39) 2g is dissolved in 10mL water (mass ratio of heteropolyacid salt and water is 2: 10), regulates pH=0.1 with hydrochloric acid (HCl), places 90 ℃ of water-baths to heat this solution, adds 1gLiCl, be cooled to room temperature after suction filtration obtain micron tube.
Embodiment 2
With α-silicotungstic acid sylvite (α-K
8SiW
11O
39) 3g is dissolved in behind the 10mL water (mass ratio of heteropolyacid salt and water is 3: 10) with phosphoric acid (H
3PO
4) regulate pH=1, place 80 ℃ of water-baths to heat this solution, add 3gCrCl
3, be cooled to room temperature after suction filtration obtain micron tube.
Embodiment 3
With α-silicotungstic acid sylvite (α-K
8SiW
11O
39) 3.5g is dissolved in behind the 10mL water (mass ratio of heteropolyacid salt and water is 3.5: 10) and regulates pH=1.5 with hydrochloric acid (HCl), places 80 ℃ of water-baths to heat this solution, adds 3gFeCl
3Mix, be cooled to room temperature after suction filtration obtain micron tube.
Embodiment 4
With α-germanotungstic acid sylvite (α-K
8GeW
11O
39) 4g is dissolved in behind the 10mL water (mass ratio of heteropolyacid salt and water is 4: 10) and regulates pH=2 with hydrochloric acid (HCl), places 70 ℃ of water-baths to heat this solution, adds 3gNiCl
2Mix, be cooled to room temperature after suction filtration obtain micron tube.
Embodiment 5
With α-silicotungstic acid sylvite (α-K
8SiW
11O
39) 5g is dissolved in behind the 10mL water (mass ratio of heteropolyacid salt and water is 5: 10) and regulates pH=3 with hydrochloric acid (HCl), places 60 ℃ of water-baths to heat this solution, adds 3gZnCl
2Mix, be cooled to room temperature after suction filtration obtain micron tube.
Claims (2)
1. the preparation method of the polyoxometallate micron tubular material of metal ion mixing is characterized in that may further comprise the steps:
(1) with unsaturated Keggin series heteropolyacid salt with 1-6: 10 mass ratio is dissolved in the water, and the pH that regulates this stock liquid is between 0-4;
(2) place 60-90 ℃ of water-bath to heat step (1) gained solution;
(3) salt that step (2) gained solution is added metal ion mixes;
(4) cooling step (3) gained solution is to room temperature, and suction filtration can obtain the POM micron tube material of metal ion mixing.
2. according to the preparation method of claim 1, it is characterized in that (1) described unsaturated Keggin series heteropolyacid salt is α-K
8SiW
11O
39, α-K
8GeW
11O
39, the salt of (3) described metal ion is LiCl, CrCl
3, FeCl
3, NiCl
2, ZnCl
2
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|---|---|---|---|
| CN201010030815A CN101774627A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polyoxometallate micron tubular material doped by metal ions |
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|---|---|---|---|
| CN201010030815A CN101774627A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polyoxometallate micron tubular material doped by metal ions |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505185A (en) * | 2011-09-29 | 2012-06-20 | 东北师范大学 | Method for preparing polyoxometallate composite mesoporous material by electrostatic spinning |
| CN103245706A (en) * | 2013-05-23 | 2013-08-14 | 北京化工大学 | SWNTs (single-walled carbon nanotubes)-IL (ionic liquid)-POM (polyoxometalate) functional composite material, and application thereof to preparation of electrochemical sensor |
| CN105618151A (en) * | 2015-12-22 | 2016-06-01 | 聊城大学 | Strontium-germanium tungsten oxygen cluster catalyst, preparation method and application of strontium-germanium tungsten oxygen cluster catalyst |
| CN107952430A (en) * | 2017-12-25 | 2018-04-24 | 聊城大学 | A kind of preparation method of double-core manganese substitution silicon tungsten oxygen cluster catalyst |
| CN114213669A (en) * | 2021-12-20 | 2022-03-22 | 东华大学 | Polyoxometallate giant surfactant and preparation method and application thereof |
-
2010
- 2010-01-13 CN CN201010030815A patent/CN101774627A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505185A (en) * | 2011-09-29 | 2012-06-20 | 东北师范大学 | Method for preparing polyoxometallate composite mesoporous material by electrostatic spinning |
| CN103245706A (en) * | 2013-05-23 | 2013-08-14 | 北京化工大学 | SWNTs (single-walled carbon nanotubes)-IL (ionic liquid)-POM (polyoxometalate) functional composite material, and application thereof to preparation of electrochemical sensor |
| CN103245706B (en) * | 2013-05-23 | 2014-12-10 | 北京化工大学 | SWNTs (single-walled carbon nanotubes)-IL (ionic liquid)-POM (polyoxometalate) functional composite material, and application thereof to preparation of electrochemical sensor |
| CN105618151A (en) * | 2015-12-22 | 2016-06-01 | 聊城大学 | Strontium-germanium tungsten oxygen cluster catalyst, preparation method and application of strontium-germanium tungsten oxygen cluster catalyst |
| CN105618151B (en) * | 2015-12-22 | 2017-12-26 | 聊城大学 | Strontium germanium tungsten oxygen cluster catalyst, preparation method and its usage |
| CN107952430A (en) * | 2017-12-25 | 2018-04-24 | 聊城大学 | A kind of preparation method of double-core manganese substitution silicon tungsten oxygen cluster catalyst |
| CN107952430B (en) * | 2017-12-25 | 2020-06-26 | 聊城大学 | Preparation method of binuclear manganese-substituted silicotungstic oxygen cluster catalyst |
| CN114213669A (en) * | 2021-12-20 | 2022-03-22 | 东华大学 | Polyoxometallate giant surfactant and preparation method and application thereof |
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Application publication date: 20100714 |