CN101733086B - Preparation and application of nano silica-base material - Google Patents
Preparation and application of nano silica-base material Download PDFInfo
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- CN101733086B CN101733086B CN 200910231739 CN200910231739A CN101733086B CN 101733086 B CN101733086 B CN 101733086B CN 200910231739 CN200910231739 CN 200910231739 CN 200910231739 A CN200910231739 A CN 200910231739A CN 101733086 B CN101733086 B CN 101733086B
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Abstract
The invention aims at providing the preparation and the application of nano silica-base material, particularly the preparation and the new application of nano silica-base material to the catalytic oxidation reaction. The nano silica-base material is in the size of 1-100nm and is nano silicon material or nano silicon alloy material or the mixture of the nano silicon material and the nano silicon alloy material. The nano silica-base material is activated by the hydrofluoric acid, and the oxidation layer on the surface of the nano silica-base material is removed, thus the nano silica-base material with the catalytic oxidation reaction activity is obtained. The nano silica-base material can be applied to the catalytic oxidation reaction at normal temperature.
Description
Technical field
The present invention relates to a kind of preparation and application of nano silica-base material, be specifically related to the application of nano silica-base material in catalytic oxidation.
Background technology
Silica-base material (such as diatomite, silica, silica gel, molecular sieve etc.) is commonly used for the carrier of catalyst in catalyst field, and the pore structure that can make catalyst obtain large active surface and be fit to increases mechanical strength and the heat endurance of catalyst.
For example, the patent No. is that the Chinese invention patent of 99107761.X discloses a kind of aldehyde liquid phase hydrogenating catalyst, and the carrier of catalyst is selected from SiO
2Or diatomite, nickel is the first active constituent, other active component is selected from cobalt, molybdenum, chromium, potassium; By weight percentage, wherein nickel content is 5-40; The content of cobalt and molybdenum is 0.2-5.0.Active component is carried by dipping or co-precipitation and is attached to SiO
2Or on the diatomite support.
The patent No. is that 94193133.1 Chinese invention patent discloses and a kind ofly prepares acrylonitrile by propylene or prepared the ammoxidation catalyst composition of methacrylonitrile by isobutene for the ammoxidation by propylene or isobutene, contain oxidation catalyst and make oxidation catalyst carry thereon silica supports, the amount of silica supports accounts for the 40-60% (wt) of oxidation catalyst and silica supports gross weight.Oxidation catalyst contains the oxide of molybdenum, bismuth, iron and component A, and component A is at least a element that is selected from potassium, rubidium and caesium, and the amount of bismuth, iron and component A represents to be respectively 0.1 to 6,0.1 to 8 and 0.01 to 0.5 with the atomic ratio of relative 12 molybdenum atoms.The preparation process of ammoxidation catalyst composition is as follows: a kind of slurry that the metallic element source consists of that forms by Ludox and oxidation catalyst is provided, this slurry of spray-drying, then calcining, wherein the aluminium content of Ludox is expressed as 0.04 or still less with the atomic ratio of relative 100 silicon atoms.
The application as catalyst in oxidation reaction has no report about silica-base material.
Summary of the invention
The object of the invention provides the new purposes of nano silica-base material, i.e. application in catalytic oxidation.
For achieving the above object, the concrete technical scheme of the present invention is, the application of nano silica-base material in catalytic oxidation, and described nano silica-base material is of a size of 1～100nm; Being selected from of described nano silica-base material: the mixture of one or more in nano silicon material or the nano-silicon alloy material.
In the technique scheme, the form of described nano silica-base material is selected from: a kind of in nano wire, nanobelt, nanometer sheet, nanotube, nanometer rods, nano whisker or the nano particle.
In the technique scheme, the crystalline form of described nano silicon material is selected from: a kind of in monocrystalline silicon, polysilicon or the unformed silicon.
In the technique scheme, described nano-silicon alloy material is selected from: a kind of in Antaciron, sige alloy or the silicon-carbon alloy.
In the prior art, common nano silica-base material surface all coats layer of oxide layer, nano silica-base material with oxide layer does not have catalytic activity, therefore, the present invention uses hydrofluoric acid to remove the oxide layer on nano silica-base material surface, nano silica-base material after hydrofluoric acid treatment has catalytic activity, can be used as the catalyst of redox reaction.
Described hydrofluoric acid treatment process specifically may further comprise the steps:
The nano silica-base material that the surface is coated oxide layer adds the solution of hydrofluoric acid, removes at normal temperatures oxide layer (reaction time is 1 second to 5 hours, determines according to the thickness of oxide layer); After separation, washing, drying, obtain having the nano silica-base material of catalytic activity.
In the technique scheme, the solution of described hydrofluoric acid comprises: the hydrofluoric acid solution of the aqueous solution of hydrofluoric acid, the alcoholic solution of hydrofluoric acid and other organic solvents; The percetage by weight of hydrofluoric acid is 0.001%～50% in the described hydrofluoric acid solution, is preferably 0.01%～30%.
Above-mentioned nano silica-base material after hydrofluoric acid treatment can be used as the catalyst of redox reaction; therefore; the claimed above-mentioned nano silica-base material of the present invention is as the application of oxidation reaction catalyst, and especially above-mentioned nano silica-base material is as the application of the catalyst of oxidation reaction under the normal temperature.
Particularly, the embodiment of the invention discloses above-mentioned nano silica-base material as the application of the standby benzoic acid of the catalyst Oxybenzene Methanol of oxidation reaction under the normal temperature, catalyzing oxidizing degrading rhodamine B, catalyzing oxidizing degrading eosin dyestuff.
Methylene blue dyestuff
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, the present invention uses hydrofluoric acid that nano silica-base material is carried out activation process, removes the oxide layer on nano silica-base material surface, has obtained to have the nano silica-base material of catalytic activity, oxidation reaction is had catalytic activity, at normal temperatures catalytic oxidation.
2, to propose first to adopt silicon be catalyst in the present invention, and the oxidation reaction that relates among the present invention is normal-temperature reaction, and at normal temperatures, catalytic effect of the present invention is than silver in the prior art, palladium, gold, rhodium catalyst effective.
Description of drawings
The scanning electron microscope (SEM) photograph of nano wire among accompanying drawing 1 embodiment one;
The scanning electron microscope (SEM) photograph of nanometer silicon chip among accompanying drawing 2 (a) embodiment two;
Uv absorption spectra among accompanying drawing 2 (b) embodiment two before and after the rhodamine B solution degradation, wherein peak height be about 1.0 for behind the catalytic oxidation 24h, peak height be about 2.1 for before the catalytic oxidation;
Uv absorption spectra among accompanying drawing 3 embodiment three before and after the rhodamine B solution degradation, wherein peak height be about 1.7 for behind the catalytic oxidation 24h, peak height be about 2.1 for before the catalytic oxidation;
Uv absorption spectra among accompanying drawing 4 embodiment four before and after the eosin dye solution degraded, wherein peak height be about 6.4 for behind the catalytic oxidation 24h, peak height be about 13.5 for before the catalytic oxidation;
Uv absorption spectra among accompanying drawing 5 embodiment five before and after the aqueous solution of methylene blue degraded, wherein peak height be about 1.8 for behind the catalytic oxidation 24h, peak height be about 3.5 for before the catalytic oxidation.
The specific embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment one
High temperature method prepares silicon nanowires 20g, and (preparation method of described nano wire is prior art, reference: [1] ST Lee, YF Zhang, N Wang, YH Tang, I Bello, CS Lee, YW Chung, J.Mater.Res.1999,14,4503.[2] MW Shao, YY Shan, NB Wong, ST Lee, Adv.Func.Mater.2005,15,1478.), this nano wire is faint yellow, and diameter (is seen Fig. 1) between 5-100nm, the kernel of silicon nanometer is the silicon of crystalline state, coated outside the unbodied silica of one deck.Process (being used for removing the silicon oxide layer of outside) after 1 minute with percetage by weight 5% hydrofluoric acid aqueous solution, join in 50 milliliters the acetonitrile solution, contain the phenmethylol of 0.2M in the acetonitrile solution, under the xenon lamp irradiation of 5W, can make benzoic acid.
Embodiment two
5 millimeters * 5 millimeters silicon chip (can be p-type or N-shaped, can be various doping contents, can be monocrystalline or polycrystalline, also can be different high preferred orientations), be placed in the plastic cup, add 10 milliliters percetage by weight 5% hydrofluoric acid ethanolic solution, add again the silver nitrate solid, to obtain the liquor argenti nitratis ophthalmicus of 0.1M concentration, under 50 degree, react half an hour to obtain silicon nanowires, this silicon nanowires is black (referring to Fig. 2 (a)).With resulting silicon chip with silicon nanowires, use again 10 milliliters 5% hydrofluoric acid alcohol solution dipping 5 minutes, join in the rhodamine B aqueous solution of 50 milliliter of 1 μ M, the degradable rhodamine B, detect with the ultra-violet absorption spectrum instrument: the degradation rate of 24h rhodamine is 50% (seeing Fig. 2 (b)).
Embodiment three
At 1 gram Antaciron nano-powder (diameter is between 30-50nm), add 30 milliliters percetage by weight 5% hydrofluoric acid ethanolic solution, after getting after 30 minutes, join again in the rhodamine B aqueous solution of 50 milliliter of 1 μ M the degradable rhodamine B.Detect with the ultra-violet absorption spectrum instrument: the degradation rate of 24h rhodamine is 20% (seeing Fig. 3).
Embodiment four
At 1 gram silicon nano power body (diameter is between 40-80nm), 5% hydrofluoric acid aqueous solution that adds 30 milliliters after getting after 1 minute, joins in the eosin solution of 50 milliliter of 1 μ M again, degradable eosin dyestuff, detect with the ultra-violet absorption spectrum instrument: the degradation rate of 24h is 50% (seeing Fig. 4).
Embodiment five
5 millimeters * 5 millimeters silicon nano thin-film is put into plastic beaker, the 5% hydrofluoric acid ethanolic solution that adds 10 milliliters, after getting after 1 minute, join again in the aqueous solution of methylene blue of 50 milliliter of 1 μ M, the degradable methylene blue dyestuff, detect with the ultra-violet absorption spectrum instrument: the degradation rate of 24h is 50% (seeing Fig. 5).
Claims (4)
1. the application of a nano silica-base material is characterized in that, nano silica-base material is as the application of oxidation reaction catalyst, and described nano silica-base material is of a size of 1～100nm; Described nano silica-base material is nano silicon material, and crystalline form is selected from: monocrystalline silicon, polysilicon or unformed silicon; Described nano silica-base material is prepared by following method, and the nano silicon material that the surface is coated oxide layer adds the solution of hydrofluoric acid, removes at normal temperatures oxide layer; After separation, washing, drying, obtain.
2. the according to claim 1 application of described nano silica-base material is characterized in that, the form of described nano silica-base material is selected from: a kind of in nano wire, nanobelt, nanometer sheet, nanotube, nanometer rods, nano whisker or the nano particle.
3. prepare the method for the described silica-base material of claim 1, it is characterized in that, specifically may further comprise the steps:
The nano silicon material that the surface is coated oxide layer adds the solution of hydrofluoric acid, removes at normal temperatures oxide layer; After separation, washing, drying, obtain having the nano silicon material of catalytic activity.
4. method according to claim 3 is characterized in that, the percetage by weight of hydrofluoric acid is 0.001%～50% in the described hydrofluoric acid solution.
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| CN 200910231739 CN101733086B (en) | 2009-12-03 | 2009-12-03 | Preparation and application of nano silica-base material |
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| CN 200910231739 CN101733086B (en) | 2009-12-03 | 2009-12-03 | Preparation and application of nano silica-base material |
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| CN101733086B true CN101733086B (en) | 2013-04-10 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474434A (en) * | 2003-07-25 | 2004-02-11 | 中国科学院上海微***与信息技术研究 | Method for producing silicon nano wire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474434A (en) * | 2003-07-25 | 2004-02-11 | 中国科学院上海微***与信息技术研究 | Method for producing silicon nano wire |
Non-Patent Citations (1)
| Title |
|---|
| 周伟民.一维碳化硅纳米材料的制备与性能的基础研究.《上海交通大学博士学位论文》.2007,第6.4.2、6.4.3、2.3.1和2.3.2节. * |
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