CN1358440A - Photo-catalyst pesticide with visible light activity and preparation process and use thereof - Google Patents
Photo-catalyst pesticide with visible light activity and preparation process and use thereof Download PDFInfo
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- CN1358440A CN1358440A CN 02114732 CN02114732A CN1358440A CN 1358440 A CN1358440 A CN 1358440A CN 02114732 CN02114732 CN 02114732 CN 02114732 A CN02114732 A CN 02114732A CN 1358440 A CN1358440 A CN 1358440A
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- titanium dioxide
- modifying titanium
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Abstract
The micriobiostatic mycocide pesticide is made of inorganic material, possesses photocatalytic activity and strong mycocidal power, and its preparation method incldues the following steps: using modified titanium dioxide suspension or modified titanium dioxide sol, highly dispersing it on the nano silicon dioxide base body to synthesize uniform titanium-silicon compound micriparticles to form suspension with Ti-O-Si reticular structure.
Description
Technical field the invention belongs to the public nuisance-free agricultural chemicals technical field, or rather, is a kind of anti-virus activities bactericide that has photocatalytic activity under visible light.
The necessary for growth of crops such as technical background vegetables, fruit tree, paddy rice is used a large amount of bactericide.The bactericide that generally uses mainly contains following a few class at present: heterocyclic, triazole type, benzene class, organic phosphates, sulphur class, copper mercury class, organotin arsenic class, antibiotic class etc.These agricultural chemicals mostly be greatly have phenyl ring, the organic compound of heterocycle structure, organic sulfur structure, organic heavy metal structure, chronic administration, residual fairly obvious in soil.Specifically, at present, mainly have following problem in the chemical pesticide use: (1) is low to the target organisms activity, because the biologically active of compound own is low or the pesticide resistance that produces because of the long term agricultural chemicals; Big to non-target organism toxicity, to the toxicity of the useful animals toxicity height of higher mammal particularly.(2) agricultural chemicals itself and degraded intermediate thereof are accumulated in environment or animal and plant body easily.(3) pesticide resistance of target organisms is obvious, need increase amount of application year by year, and agricultural environment is subjected to more and more serious pesticide pollution, and the agricultural product residue of pesticide exceed standard seriously, and therefore greatly reduces agricultural products in China competitiveness in the international market.(4) broad spectrum activity is poor, and a kind of agricultural chemicals is often only effective to a certain or several middle diseases.
Therefore, the public nuisance-free agricultural chemicals formulation of new efficient, the low toxicity of exploitation, low-residual, wide spectrum is imperative.
The purpose of this invention is to provide a kind of efficient, nontoxic, bacterium and fungus disease are had anti-virus activities bactericide broad spectrum activity, that have plant protection and environmental protection double effects.
Summary of the invention photo-catalyst pesticide of the present invention is made up of the inorganic material of no side effects, these inorganic material are inorganic ions such as titanium dioxide, silica, iron ion, modifying titanium dioxide etc., titanium dioxide and silica can be micron-sized, or nano level.Modifying titanium dioxide has been compound tungstic acid, di-iron trioxide, manganese dioxide, the titanium dioxide of compounds such as zinc oxide, or mixed iron ion, the titanium dioxide of metal ions such as copper ion, the difference of these modifying titanium dioxides and pure titinium dioxide is, modifying titanium dioxide can be by excited by visible light, under visible light, has photocatalytic activity, and has a sterilizing function, photo-catalyst pesticide of the present invention be with modifying titanium dioxide suspension or modifying titanium dioxide colloidal sol high degree of dispersion on the nanometer titanium dioxide silicon substrate, synthetic uniform titanium-silicon composite particles, formation has the cancellated suspension of Ti-O-Si.
The preparation method of photo-catalyst pesticide of the present invention comprises the steps:
1) preparation of modifying titanium dioxide suspension:
The modifying titanium dioxide particle is a raw material, modifying titanium dioxide is to use Detitanium-ore-type, it also can be rutile-type, be preferably the Detitanium-ore-type particle, this particle can be nano level also can be micron-sized, most preferably be the particle of 5-20 nanometer particle size, preparation technology: the modifying titanium dioxide powder is dispersed in the ethanol, and the mol ratio of modifying titanium dioxide and ethanol is 1-5: 50-500; Preferred proportion is 1: 75-100,
2) preparation of modifying titanium dioxide colloidal sol:
With titanate ester such as butyl titanate, metatitanic acid, titanyl sulfates etc. are raw material, mix the titanium colloidal sol of metal ions such as iron ion, its preparation technology: at room temperature titanate ester is joined in the absolute ethyl alcohol, it is 0.5%-5% nitric acid that stirring and quick adding contain concentration, 0.05-0.07 the ferric nitrate of mol (or iron sulfate) aqueous solution, obtained titanium colloidal sol in vigorous stirring 20-30 minute, titanate esters, the volume ratio of absolute ethyl alcohol and iron nitrate solution is 3-10: 30-90: 0.5-3, preferred ratio is 4-6: 50-60: 1-1.5, and the concentration content of nitric acid is preferably 2%.
3) preparation of silica substrate:
Silica substrate is the silica with nano-scale that the Ludox hydrolysis produces, Ludox preparation technology: 40 ℃ with silicate class such as butyl silicate and absolute ethyl alcohol with 30-50: the 50-60 volume ratio is mixed, stirred 0.5-1 hour, obtain Ludox, the preferred volume ratio of silicate class and absolute ethyl alcohol is 1: 1.5-2.
4) have the preparation of the cancellated composite particles of Ti-O-Si:
Being that modifying titanium dioxide particulate load in the modifying titanium dioxide suspension produces on the silicon dioxide colloid matrix, also can be that the modifying titanium dioxide colloidal particle in the titanium colloidal sol is carried on the composite particles that produces on the silicon dioxide colloid matrix.Preparation technology: modifying titanium dioxide suspension or modifying titanium dioxide colloidal sol (being above-mentioned 1) or 2) prepared in), with prepared in the silicon dioxide gel (being above-mentioned 3)) mix, stirred 1-2 hour, add mixed liquor volume 5%-15% surfactant Tween-40 again, mixing, get final product, the mol ratio of titanium dioxide and silica is 1: 0.1-10, preferred proportion are 1: 1-5.Prepared titanium-silicon the composite particles of the present invention not only has the Ti-O-Si network structure, and simultaneously, this composite particles has stronger hydrophily.
Sterilizing mechanisms of the present invention is under the effect of sunshine, and the titanium dioxide in the bactericide is excited, and produces the extremely strong hydroxyl radical free radical of oxidability, and it can kill bacterium, fungi, the actinomycetes that touch to non-selectivity.
Antibacterial principle of the present invention is: silica and titanium oxide have hydrophilic, and the hydrophobicity on crop leaf surface weakens, and hydrophily strengthens greatly, have changed the topological structure on crop leaf surface; Suppress the release of the outer material of fungal spore born of the same parents, suppress the adhesive attraction of germ spore, make the sporoducts of germ and adhere to spore to be difficult to form on the crop leaf surface on the crop leaf surface.Thereby, prevent of the infection of external germ to crop.
The advantage of the photo-catalyst agent of indication of the present invention mainly contains:
(1) inorganic compound cheapness, no side effects such as used titanium dioxide, silica, have higher biochemistry inertia, can not cause murder by poisoning to non-target organism, can not bring pollution, particularly on vegetables and fruit tree, have important use and be worth to agricultural environment.
(2) titanium dioxide is scattered on the cataloid carrier, the Ti/Si composite particles forms the Ti-O-Si network structure, help the right separation in titanium dioxide photoproduction electronics one hole and the raising of quantum efficiency, its catalysis bactericidal activity is higher than the pure titinium dioxide particle, simultaneously do not destroy the crop leaf cuticula, obviously improve plant resistance to environment stress.
(3) use modifying titanium dioxide as optical active substance, can be by excited by visible light, overcast and rainy effectively same, high humility can also provide bactericidal effect.In sum, the present invention uses safety such as titanium dioxide, silica, cheap, free of contamination inorganic material, is a kind of environmental type bactericide with DEVELOPMENT PROSPECT, is a kind of novel photocatalysis agricultural chemicals.
Raw material of the present invention all is commercially available prod.
The bactericide of indication of the present invention can be widely used in the bacterium of various greenhouses and field crop, the control of fungus disease, is suitable for the control of the disease on vegetables, the fruit tree especially.
Embodiment
Embodiment 1
20 gram Germany are produced in the ethanol that P-25 type titanium dioxide powder are scattered in 1000 milliliter 95%, and powerful the stirring 1-2 hour obtains suspension A; Under 40 ℃, 73 milliliters of tetraethoxysilances are mixed with 100 milliliters of absolute ethyl alcohols, stirred 0.5-1 hour, obtain Ludox B; Suspension A is mixed with Ludox B, and adding volume ratio is 10% Tween-40, stirs, and makes 1: 4 composite photocatalyst sterilization colloidal sol of Ti/Si mol ratio.
Embodiment 2
Be that the titanium dioxide powder of 2% tungstic acid is scattered in 1000 milliliter 95% the ethanol with the compound mol ratio of 20 grams, the powerful stirring 1-2 hour obtains suspension A; Under 40 ℃, 73 milliliters of tetraethoxysilances are mixed with 100 milliliters of absolute ethyl alcohols, stirred 0.5-1 hour, obtain Ludox B; Suspension A is mixed with Ludox B, add this and amass, stir, make 1: 4 complex sol of Ti/Si mol ratio than being 10% Tween-40.
Embodiment 3
It is that the titanium dioxide powder of 0.5% iron ion is scattered in 1000 milliliter 95% the ethanol that 20 grams have been mixed mol ratio, and powerful the stirring 1-2 hour obtains suspension A; Under 40 ℃, 73 milliliters of tetraethoxysilances are mixed with 100 milliliters of absolute ethyl alcohols, stirred 0.5-1 hour, obtain Ludox B; Suspension A is mixed with Ludox B, and adding volume ratio is 10% Tween-40, stirs, and makes 1: 4 complex sol of Ti/Si mol ratio.Embodiment 4
It is 4% aqueous solution of nitric acid that the iron nitrate aqueous solution of 5 milliliter of 0.2 mol is joined 5 ml concns, obtains solution A; 34 milliliters of butyl titanates are added drop-wise in 340 milliliters of absolute ethyl alcohols stir, add solution A fast, vigorous stirring obtains the titanium sol B; Under 40 ℃ of constant temperatures, 29.2 milliliters of tetraethoxysilances and 60 milliliters of absolute ethyl alcohols are mixed stirring 1.0 hours, obtain Ludox C; The titanium sol B is mixed with Ludox C, and adding volume ratio is 10% Tween-40, stirs, and makes 1: 4 complex sol of Ti/Si mol ratio.
Embodiment 5
It is 4% aqueous solution of nitric acid that the iron nitrate aqueous solution of 10 milliliter of 0.2 mol is joined 10 ml concns, obtains solution A; 68 milliliters of butyl titanates are added drop-wise in 600 milliliters of absolute ethyl alcohols stir, add solution A fast, vigorous stirring obtains the titanium sol B; Under 40 ℃ of constant temperatures, 29.2 milliliters of tetraethoxysilances and 60 milliliters of absolute ethyl alcohols are mixed stirring 1.0 hours, obtain Ludox C; The titanium sol B is mixed with Ludox C, and adding volume ratio is 10% Tween-40, stirs, and makes 1: 2 complex sol of Ti/Si mol ratio.
Claims (8)
1. photo-catalyst pesticide with visible light activity, form by inorganic material titanium dioxide, silica, iron ion inorganic ions, modifying titanium dioxide, it is characterized in that modifying titanium dioxide colloidal sol is dispersed on the nm TiO 2-base body, synthetic uniform titanium-silicon composite particles, formation has the cancellated suspension of Ti-O-Si.
2. according to the agricultural chemicals described in the claim 1, the titanium dioxide of tungstic acid, di-iron trioxide, manganese dioxide, zinc oxide or doped metal ion that it is characterized in that described modifying titanium dioxide has been compound.
3. a method for preparing agricultural chemicals described in the claim 1 is characterized in that comprising the steps:
1) preparation of modifying titanium dioxide suspension:
Nanoscale or micron order modifying titanium dioxide powder are dispersed in the ethanol, and modifying titanium dioxide and ethanol mol ratio are 1-5: 50-500;
2) preparation of modifying titanium dioxide colloidal sol:
At room temperature titanate ester is joined in the absolute ethyl alcohol, stir to add down and contain the iron nitrate aqueous solution that concentration is 0.5%-5% nitric acid, stir and made in 20-30 minute, the volume ratio of titanate ester, absolute ethyl alcohol and iron nitrate solution is 3-10: 30-90: 0.5-3;
3) preparation of silica substrate:
Under 40 ℃ silicate class and absolute ethyl alcohol are mixed with volume ratio 30-50: 50-60, stirred 0.5-1 hour, obtaining Ludox is silica substrate;
4) have the preparation of the cancellated composite particles of Ti-O-Si:
Above-mentioned 1) or 2) in modifying titanium dioxide suspension or modifying titanium dioxide colloidal sol and above-mentioned 3) in Ludox mix, stirred 1-2 hour, the surfactant that adds mixed liquor volume 5%-15% can make, and the mol ratio of titanium dioxide and silica is 1: 0.1-10.
4. according to the method described in the claim 3, it is characterized in that described 1) in the modifying titanium dioxide powder be rutile-type or Detitanium-ore-type, powder is preferably 5-20 nanometer particle size particle, modifying titanium dioxide and ethanol mol ratio are 1: 25-100.
5. according to the method described in the claim 3, it is characterized in that described 2) in the volume ratio of raw material titanate ester, absolute ethyl alcohol and iron nitrate solution of TiO 2 sol be 4-6: 50-60: 1-1.5, molysite can be an iron sulfate also, and nitric acid content is 2% in the molysite.
6. according to the method described in the claim 3, it is characterized in that described 3) volume ratio of mesosilicic acid ester class and absolute ethyl alcohol is 1: 1: 5-2.
7. according to the method described in the claim 3, it is characterized in that described 4) in surfactant be Tween-40, the mol ratio of titanium dioxide and silica is 1: 1-5.
8. the purposes of the agricultural chemicals described in the claim 1 is characterized in that the sterilization as field crop and chamber crop, in particular as the sterilization of vegetables, fruit tree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 02114732 CN1358440A (en) | 2002-01-14 | 2002-01-14 | Photo-catalyst pesticide with visible light activity and preparation process and use thereof |
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| CN 02114732 CN1358440A (en) | 2002-01-14 | 2002-01-14 | Photo-catalyst pesticide with visible light activity and preparation process and use thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295003C (en) * | 2003-11-20 | 2007-01-17 | 上海交通大学 | Preparation of self-catalyze degradation pesticide |
| CN102583399A (en) * | 2012-01-13 | 2012-07-18 | 东华大学 | Preparation method for cubic Si-O-Ti composite particles |
| CN104072955A (en) * | 2013-03-26 | 2014-10-01 | 上海杰事杰新材料(集团)股份有限公司 | An antibacterial polylactic acid composite material and a preparing method thereof |
| CN104430520A (en) * | 2014-10-24 | 2015-03-25 | 苏州科大微龙信息技术有限公司 | Titanium-sulfur powdery mildew prevention mixture |
| CN104688773A (en) * | 2005-10-26 | 2015-06-10 | Toto株式会社 | Cell killer |
| CN105016382A (en) * | 2014-04-30 | 2015-11-04 | 中国科学院化学研究所 | Method for preparing pure gold redstone type titanium dioxide nanorod |
| CN105191987A (en) * | 2015-09-16 | 2015-12-30 | 苏州科大微龙农业科技有限公司 | Nano-titanium and biological-sulfur-zinc-manganese mixture for melon powdery mildew |
| CN106561710A (en) * | 2016-11-08 | 2017-04-19 | 佛山市铁人环保科技有限公司 | Titanium dioxide sol capable of degrading pesticide residues, and preparation method of titanium dioxide sol |
| CN106577731A (en) * | 2016-12-05 | 2017-04-26 | 中国科学院成都生物研究所 | Antibacterial application of titanium ion of variable valence with light energy |
| CN107583652A (en) * | 2017-10-20 | 2018-01-16 | 江苏高淳陶瓷股份有限公司 | A kind of mesoporous silicon oxide photocatalysis net and preparation method |
| CN107603316A (en) * | 2017-09-08 | 2018-01-19 | 常州达奥新材料科技有限公司 | A kind of preparation method of antifogging self-cleaning nano material |
| CN109077063A (en) * | 2018-08-16 | 2018-12-25 | 乐山师范学院 | A kind of titania-silica micro mist and its preparation method and application |
| CN113795149A (en) * | 2019-04-04 | 2021-12-14 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
-
2002
- 2002-01-14 CN CN 02114732 patent/CN1358440A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295003C (en) * | 2003-11-20 | 2007-01-17 | 上海交通大学 | Preparation of self-catalyze degradation pesticide |
| CN104688773A (en) * | 2005-10-26 | 2015-06-10 | Toto株式会社 | Cell killer |
| CN104688773B (en) * | 2005-10-26 | 2017-11-03 | Toto株式会社 | Cytocide |
| CN102583399A (en) * | 2012-01-13 | 2012-07-18 | 东华大学 | Preparation method for cubic Si-O-Ti composite particles |
| CN104072955B (en) * | 2013-03-26 | 2017-06-27 | 上海杰事杰新材料(集团)股份有限公司 | A kind of antibacterial polylactic acid composite and preparation method thereof |
| CN104072955A (en) * | 2013-03-26 | 2014-10-01 | 上海杰事杰新材料(集团)股份有限公司 | An antibacterial polylactic acid composite material and a preparing method thereof |
| CN105016382A (en) * | 2014-04-30 | 2015-11-04 | 中国科学院化学研究所 | Method for preparing pure gold redstone type titanium dioxide nanorod |
| CN105016382B (en) * | 2014-04-30 | 2017-01-11 | 中国科学院化学研究所 | Method for preparing pure gold redstone type titanium dioxide nanorod |
| CN104430520A (en) * | 2014-10-24 | 2015-03-25 | 苏州科大微龙信息技术有限公司 | Titanium-sulfur powdery mildew prevention mixture |
| CN105191987A (en) * | 2015-09-16 | 2015-12-30 | 苏州科大微龙农业科技有限公司 | Nano-titanium and biological-sulfur-zinc-manganese mixture for melon powdery mildew |
| CN106561710A (en) * | 2016-11-08 | 2017-04-19 | 佛山市铁人环保科技有限公司 | Titanium dioxide sol capable of degrading pesticide residues, and preparation method of titanium dioxide sol |
| CN106577731A (en) * | 2016-12-05 | 2017-04-26 | 中国科学院成都生物研究所 | Antibacterial application of titanium ion of variable valence with light energy |
| CN106577731B (en) * | 2016-12-05 | 2019-04-19 | 中国科学院成都生物研究所 | The antibacterial application of luminous energy transition-metal ions titanium |
| CN107603316A (en) * | 2017-09-08 | 2018-01-19 | 常州达奥新材料科技有限公司 | A kind of preparation method of antifogging self-cleaning nano material |
| CN107583652A (en) * | 2017-10-20 | 2018-01-16 | 江苏高淳陶瓷股份有限公司 | A kind of mesoporous silicon oxide photocatalysis net and preparation method |
| CN109077063A (en) * | 2018-08-16 | 2018-12-25 | 乐山师范学院 | A kind of titania-silica micro mist and its preparation method and application |
| CN109077063B (en) * | 2018-08-16 | 2021-02-12 | 乐山师范学院 | Titanium dioxide-silicon dioxide micro powder and preparation method and application thereof |
| CN113795149A (en) * | 2019-04-04 | 2021-12-14 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
| CN113795149B (en) * | 2019-04-04 | 2023-12-12 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
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