CN1504555A - Purpose for modified photocatalyst nanometer composite material - Google Patents
Purpose for modified photocatalyst nanometer composite material Download PDFInfo
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- CN1504555A CN1504555A CNA021536015A CN02153601A CN1504555A CN 1504555 A CN1504555 A CN 1504555A CN A021536015 A CNA021536015 A CN A021536015A CN 02153601 A CN02153601 A CN 02153601A CN 1504555 A CN1504555 A CN 1504555A
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Abstract
The invention relates to the field of photo-catalytic nano composite material, wherein the modified photo-catalytic nano composite material is used to degrade the residual pesticides in vegetables, amphisarca and agronomic crops whose process comprises, diluting the water-soluble solution of the modified photo-catalytic nano material using 2-10 times of water, spraying it directly onto the surface of vegetables, amphisarca, or agronomic crops, wherein the content of nano titanium dioxide in the modified photo-catalytic nano material is 2-0.05mol/L, the content of metallic ion is 0.2-1.0 times 10 to the power of -4 mol/L, the content of water-soluble oxidation agent is 30-0.5wt%.
Description
Technical field
The invention belongs to the photo-catalytic nano field of compound material, particularly a kind of purposes of utilizing the degraded of modified photocatalyst nano composite material to remove the remains of pesticide in vegetables, melon and fruit or the farm crop etc.
Background technology
Along with the raising of people's living standard, increasing people no longer has been confined on quantity and the kind the demand of goods for consumptions such as daily required vegetables, fruit, tealeaves, but the green safety of goods for consumption is had higher requirement.People recognize that more and more the organic pesticide that remains on the goods for consumptions such as vegetables, fruit, tealeaves not only can work the mischief to human body, and because excessive use agricultural chemicals, the harmful agricultural chemicals that remains in the soil has played very big destruction to environment.Therefore, the product of developing remains of pesticide in economic, practical, wide spectrum, long lasting removing or the degraded farm crop has good market outlook, and benefits the nation and the people, and good social benefit and economic benefit are arranged.At present, existing many research institutions and personnel are studying the method and the technology of remains of pesticide in removing or the degraded farm crop.Through data-searching, existing some relevant being used for are removed or the reagent and the other products of the farm crop remains of pesticide of degrading are interviewed.For example, denomination of invention: " eliminating agent for chemical left over from vegetable ", and application number: 91108315.4, open day: 1992.03.25; This disclosure of the Invention a kind of vegetable and fruit eliminating agent for chemical left over, selecting nitre, alkali, salt, alum for use is raw material.Denomination of invention: " vegetables, fruit cleaning agent of remanent pesticide ", application number: 91109223.4, open day: 1992.04.01; This invention provides a kind of vegetables, fruit cleaning agent of remanent pesticide that adds tensio-active agent and add compositions such as complexing agent and clorox.Denomination of invention: " detergent for removing farm chemical remained on vegetable and fruit ", application number: 95117069.4, open day: 1997.01.08; This invention is a kind of clean-out system that is used to clean residual agricultural chemicals from vegetable or fruit, and it contains nonionic polyoxyalkylene surface active agent modified silicon oil and sucrose monolaurate, solvent propylene glycol, alkaline assistant yellow soda ash and sodium bicarbonate and water.Denomination of invention: " plant type multi-function is removed harmful residual of agricultural chemical on vegetable and fruit liquid ", application number: 96122348.0, open day: 1998.05.27; This invention be plant type multi-function remove harmful residual of agricultural chemical on vegetable and fruit liquid system by several to twenties kind of plant after a series of processing, step mixes by a certain percentage.Have dissolving fruit and vegetable surfaces wax layer, decompose residual toxicity, affinely go out residual toxicity in the fruits and vegetables, clean and remove the pesticidal toxin function.Denomination of invention: " removing the method for pesticide residue on picked melon and fruit and the clean-out system of use ", application number: 00117746.X, open day: 2001.01.31; This invention is a kind ofly to adopt zymin to remove pesticide residue on picked melon and fruit, improve the method for fruit and vegetable quality, is to adopt papoid or/and Bromenzyme was invested in the fruit and vegetable of immersion 5-15 minute, washes down with clear water again.But, existing method and product exist effect not significantly, cost is high, range of application is little, use is inconvenient, secondary pollution problems is arranged.
Photocatalyst material is that a class is the general name of the functional material with photocatalysis of representative with titanium dioxide.The titanium dioxide of anatase crystal can produce free electron and hole under ultraviolet irradiation, thereby has a very strong photoxidation restoring function, various organic compound of oxidable decomposition and part inorganics, can destroy the cytolemma of bacterium and solidify the protein of virus, have the function of extremely strong antifouling, sterilization, deodorizing and antiultravioletization.The existing a large amount of research report about photocatalyst of titanium dioxide material photoxidation restoring function of developed country such as the U.S., Japan is delivered, and function and its practical value that has that the titanium dioxide of anatase crystal has very strong photocatalysis have been the fact that need not suspect.Because the purposes of photocatalyst aspect environmental purification be wide, have a far reaching influence, be called as light and purify revolution.Japan is the country of photocatalyst technological precedence, has reached the practicability level in antifouling, antibiotic, deodorizing, purifying air, water wetted material, water treatment, degradable plastics and environmental protection etc. aspect many in recent years, and forms the industry of considerable scale.Though existing researchist utilizes the photocatalyst technology both at home and abroad, the technical study of remains of pesticide in doing the degraded farm crop, but up to the present, all also do not utilize the product of remains of pesticide in the removal of photocatalyst of titanium dioxide material making or the farm crop of degrading to emerge both at home and abroad.
At present, commercially available photocatalyst of titanium dioxide material must use in the presence of the illumination below the 380nm and oxygen and moisture, and competence exertion goes out tangible effect, and range of application is restricted.Under the illumination condition of daylight source, commercially available photocatalyst of titanium dioxide starting material poor activity, photocatalysis efficiency is low, and the effect of product is not remarkable.Modifying titanium dioxide photo-catalytic nano properties of materials is, when the water-soluble glue liquid solution of preparing titanium dioxide, after adding a certain proportion of promoting agent, can improve the activity of photocatalyst of titanium dioxide, improve its photocatalysis efficiency, make it under the illumination condition of common daylight source, very high photocatalysis efficiency is also arranged, reach the effect that remains of pesticide is removed in significant degraded.
Summary of the invention
The objective of the invention is to overcome existing degraded remove remains of pesticide product in vegetables, melon and fruit or the farm crop etc. exist effect not significantly, cost is high, range of application is little, use is inconvenient, defective such as secondary pollution is arranged, provide a kind of activation modification photo-catalytic nano material new purposes, be used for degrading and remove remains of pesticide in vegetables, melon and fruit or the farm crop etc.
Activation modification photo-catalytic nano material of the present invention is to utilize the photo-catalytic nano material to have the characteristic of photo-catalysis function, after its process catalytic activity modification processing, it can be decomposed or DeR by the photochemical catalysis agricultural chemicals under the irradiation that contains light sources such as ultraviolet visible light, thereby remove the agricultural chemicals that remains on vegetables, melon and fruit or the farm crop etc.
Modified photocatalyst nano material of the present invention is the water-soluble glue liquid solution, be made up of the outstanding muddy water solution of nano titanium dioxide powder or the water-soluble glue liquid solution of nano titanium oxide, the aqueous solution that contains transition metal ion and water-soluble oxidizers, wherein the content of nano titanium oxide is 2～0.05mol/L in the modified photocatalyst nano material; The content of metal ion is 0.2～1.0 * 10
-4Mol/L; The content of water-soluble oxidizers is 30～0.5wt%;
Described transition metal comprises elements such as zinc, chromium, iron or copper;
Described water-soluble oxidizers comprises Peracetic Acid or hydrogen peroxide etc.
Modified photocatalyst preparation of nanomaterials of the present invention, this method steps comprises:
(1). the preparation of the water-soluble glue liquid solution of nano titanium dioxide powder:
A. directly select commercially available Nano titanium dioxide powder for use, add in the water solvent, obtain the outstanding muddy water solution of Nano titanium dioxide after the stirring;
Or
B. directly select the water-soluble glue liquid solution of commercially available nano titanium oxide for use;
(2). at room temperature, the aqueous solution that in the water-soluble glue liquid solution of outstanding muddy water solution of the Nano titanium dioxide of step (1) or nano titanium oxide, adds transition metal ion, stir, obtain mixing solutions, wherein the content of metal ion is 0.2～1.0 * 10 in the mixing solutions
-4Mol/L, the content of nano titanium oxide are 2～0.05mol/L;
(3). at room temperature, add water-soluble oxidizers in the mixing solutions of step (2), stir, make the water-soluble glue liquid solution of modified photocatalyst nano material, wherein the content of metal ion is 0.2～1.0 * 10 in the modified photocatalyst nano material
-4Mol/L, the content of nano titanium oxide are 2～0.05mol/L, and the content of water-soluble oxidizers is 30～0.5wt%.
The purposes of modified photocatalyst nano material of the present invention, described modified photocatalyst nano material are used for degrading and remove the remains of pesticide of vegetables, melon and fruit or farm crop etc.
With 2～10 times water the water-soluble glue liquid solution of modified photocatalyst nano material is diluted to desired concn, directly spray in the surface of vegetables, melon and fruit or farm crop etc., perhaps after in the immersion solution such as vegetables, melon and fruit or farm crop, extract immediately, at natural light or contain and get final product after shining 10～30 minutes under the light source of UV-light.
The present invention utilizes activation modification photo-catalytic nano material degradation to remove vegetables, the technological method of the remains of pesticide in melon and fruit or the farm crop etc. is, for pesticide-tainted vegetable, melon and fruit or farm crop etc., before it is collected from the farmland, or before edible at home the cleaning, the water-soluble glue liquid solution of photo-catalytic nano material of preparation is sprayed at the surface of farm crop, after natural light or other contain ultraviolet light source irradiation, utilize the ability of the photochemical catalytic oxidation reduction reaction that the photocatalyst of titanium dioxide material produces after rayed, decompose the various organic compound ingredients in the agricultural chemicals, thereby will remain in vegetables, the agricultural chemicals on surface such as melon and fruit or farm crop decomposes, be converted into nontoxic material, play and remove or the toxic effect of degrading pesticide.
Modified photocatalyst nano material provided by the invention is nontoxic, harmless, preparation technology is simple, to no any damages such as vegetables, melon and fruit or farm crop, both made under the illumination condition of common daylight source, very high photocatalysis efficiency is also arranged, can reach significant degraded and remove the effect of remains of pesticide, and have both antibiotic and sterilizing is arranged, the effect of disease-resisting, insecticidal.Producing and the equal non-environmental-pollution of use, meet requirements of green environmental protection fully.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed elaboration.
Embodiment 1.
At room temperature, take by weighing CYC-701 (Chengyin Hi-Tech Co., Ltd., Shenzhen) the nano titania level powder of 0.5g, put into the Glass Containers of 1L, add the distilled water of 500ml, be made into the titania solution of 1g/L; Get hydrogen peroxide (30wt%) 167ml, become 500ml, make the hydrogen peroxide of 10wt% with distilled water diluting; Take by weighing the FeCl of 7.2g
36H
20, be dissolved among the HCl (1mol/L) of 83ml, with distilled water diluting to 500ml; Above three kinds of solution by after mixing, stir with volume, are mixed with the outstanding muddy water solution of modified photocatalyst nano material.
Embodiment 2.
With the outstanding muddy water solution of the modified photocatalyst nano material of embodiment 1, choose branch in the structure tropeolin-D close, methyl orchid with agricultural chemicals, Congo redly be target compound, carry out the degradation of pesticide preliminary experiment.
2.1 prepare commercially available tropeolin-D, methyl orchid, Congo red (concentration is 0.1g/L), every sample is got 3ml, adds the degradation agents 9ml with embodiment 1 preparation in every part of sample, in UV-light 35～36uw/cm
2Condition under shine 0,10,20,30,40,50,60 minute respectively after, use the S22PC spectrophotometer, measure its absorbancy under the wavelength at maximum absorption band place separately at it, and be benchmark with the indicator solution that does not add degradation agents, calculate degradation efficiency.
2.2 measurement result is as shown in the table:
| Time (branch) | ??10 | ??20 | ??30 | ??40 | ??50 | ??60 | |
| Degradation efficiency (%) | Tropeolin-D | ??36.00 | ??62.78 | ??87.35 | ??91.83 | ??93.43 | ??93.55 |
| The methyl orchid | ??28.02 | ??44.37 | ??56.32 | ??65.55 | ??71.93 | ??73.96 | |
| Congo red | ??59.44 | ??65.73 | ??67.03 | ??72.45 | ??77.22 | ??76.25 | |
2.3 conclusion: the degradation agents with the present invention's preparation has tangible Degradation for organic compound.
Embodiment 3.
With the outstanding muddy water solution of the modified photocatalyst nano material of embodiment 1 degradation experiment to various pesticidal solutions.
Choose commercially available organophosphorus commonly used or carboxylamine agricultural chemicals, be mixed with certain density pesticidal solutions, the outstanding muddy water solution of the modified photocatalyst nano material of embodiment 1 is mixed with organophosphorus or carboxylamine pesticidal solutions, adopt the remains of pesticide tacheometer to detect its degradation effect after the DeR.
3.1 determining instrument: PR2000A type pesticide residue rapid detector (Shenzhen Ying Sitai scientific and technological development company limited product), adopt the monolithic computer to carry out temperature-time control, cooperate the acetylcholinesterase test paper to carry out fast and convenient qualitative test the pesticide residue of vegetables, fruit and other food.But the detection principle of this tacheometer is a Pseudocholinesterase catalysis indigo powder acetic ester (redness) is hydrolyzed to acetate and indigo powder (blueness), organophosphorus or carboxylamine agricultural chemicals have restraining effect to Pseudocholinesterase, the process of catalysis, hydrolysis, variable color is changed, can judge the existence that whether contains organophosphorus or carbamate chemicals for agriculture in the sample thus.
3.2 experimental procedure: nine kinds of agricultural chemicals (concentration such as table 1) of preparation different concns, the outstanding muddy water solution of modified photocatalyst nano material of getting 1.5ml embodiment 1 is in test tube, the pesticidal solutions that adds the 0.5ml different concns, after mixing, be 40 μ w/cm at 22.5 ℃ of temperature, humidity 77%, ultraviolet ray intensity
2Condition under placed 30 minutes, adopt PR2000A type pesticide residue rapid detector to detect its degradation effect, result such as table 1 then.
Table 1
| Pesticide name | Blank distilled water | Trichlorphon | SD-1750 | Rogor | Isofenphos_methyl | The Malathion | Isocarbophos | Volaton | Omethoate | Acephate |
| Concentration (ppm) | 300 | 500 | 500 | 200 | 300 | 200 | 500 | 200 | 800 | |
| Before adding the modified photocatalyst nano material | Blue | Canescence | Canescence | Canescence | Canescence | Canescence | Canescence | Canescence | Canescence | Canescence |
| After adding the modified photocatalyst nano material | Blue | Blue | Blue | Blue | Blue | Blue | Blue | Blue | Blue | Blue |
3.3 conclusion: the result shows that the pesticidal solutions of nine kinds of different concns is all degraded.
Annotate: 1. compare white tablet nondiscoloration or the slightly light blue positive findings that is with the blank card; The white tablet becomes sky blue or identical with the blank card, negative result.
2. sensitivity index: the detection limit of quick measuring card is generally 1ppm.
Embodiment 4.
With the outstanding muddy water solution of the modified photocatalyst nano material of embodiment 1 degradation experiment to remains of pesticide on the vegetables.
With the heart of a cabbage is example.Choose commercially available organophosphorus commonly used or carboxylamine agricultural chemicals, be mixed with certain density pesticidal solutions, after being sprayed at pesticidal solutions on the heart of a cabbage surface, again with the outstanding muddy water spray solution of the modified photocatalyst nano material of embodiment 1 on the heart of a cabbage surface, adopt the remains of pesticide tacheometer to detect its degradation effect after the DeR.
4.1 determining instrument: PR2000A type pesticide residue rapid detector (Shenzhen Ying Sitai scientific and technological development company limited product), adopt the monolithic computer to carry out temperature-time control, cooperate the acetylcholinesterase test paper to carry out fast and convenient qualitative test the pesticide residue of vegetables, fruit and other food.But the detection principle of this tacheometer is a Pseudocholinesterase catalysis indigo powder acetic ester (redness) is hydrolyzed to acetate and indigo powder (blueness), organophosphorus or carboxylamine agricultural chemicals have restraining effect to Pseudocholinesterase, the process of catalysis, hydrolysis, variable color is changed, can judge the existence that whether contains organophosphorus or carbamate chemicals for agriculture in the sample thus.
Detecting instrument and principle such as embodiment 3.
4.2 experimental procedure: get three parts of each 100g of fresh heart of a cabbage, after spraying SD-1750, Trichlorphon, three kinds of different pesticidal solutions of acephate respectively, the outstanding muddy water solution of the modified photocatalyst nano material of sprinkling embodiment 1 is 632 μ w/cm at 26.5 ℃ of temperature, humidity 59%, ultraviolet ray intensity on the heart of a cabbage surface
2Condition under place after 30 minutes, get each 5g of heart of a cabbage blade tip in 3 small beakers, each adds 10ml distilled water all is capped the dish leaf, shakes on ultrasonic oscillator 3 minutes, makes leaching liquid.Every kind of leaching liquid got three parts, and every part of 0.5ml measures its degradation effect, result such as table 2 with the rapid determination instrument in small test tube.
Table 2
| Blank | Former cabbage heart | Spray Trichlorphon | The spray dichlorvos | The spray acephate | |
| No modified photocatalyst nano material | Blue | Greyish white (band is blue slightly) | Greyish white | Greyish white | Greyish white |
| Add the modified photocatalyst nano material | Blue | Blue | Blue | Blue | Blue |
4.3 conclusion: remains of pesticide is degraded.
Annotate: 1. compare white tablet nondiscoloration or the slightly light blue positive findings that is with the blank card; The white tablet becomes sky blue or identical with the blank card, negative result.
2. sensitivity index: the detection limit of quick measuring card is generally remains of pesticide 1ppm.
Claims (5)
1. the purposes of a modified photocatalyst nano composite material is characterized in that: described modified photocatalyst nano material is used for degrading and removes the remains of pesticide of vegetables, melon and fruit or farm crop.
2. purposes as claimed in claim 1, it is characterized in that: described modified photocatalyst nano material be used for the degrading remains of pesticide of removing vegetables, melon and fruit or farm crop is to dilute with 2～10 times water outstanding muddy water solution or the water-soluble glue liquid solution with the modified photocatalyst nano material, directly spray in the surface of vegetables, melon and fruit or farm crop, extract immediately after perhaps immersing vegetables, melon and fruit or farm crop in the solution, at natural light or contain under the light source of UV-light and shone 10～30 minutes.
3. purposes as claimed in claim 1 or 2, it is characterized in that: described modified photocatalyst nano material is the water-soluble glue liquid solution, be made up of the outstanding muddy water solution of Nano titanium dioxide powder or the water-soluble glue liquid solution of nano titanium oxide, the aqueous solution that contains transition metal ion and water-soluble oxidizers, wherein the content of nano titanium oxide is 2～0.05mol/L in the modified photocatalyst nano material; The content of metal ion is 0.2～1.0 * 10
-4Mol/L; The content of water-soluble oxidizers is 30～0.5wt%.
4. purposes as claimed in claim 3 is characterized in that: described transition metal comprises zinc, chromium, iron or copper.
5. purposes as claimed in claim 3 is characterized in that: described water-soluble oxidizers comprises Peracetic Acid or hydrogen peroxide.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342784C (en) * | 2006-03-15 | 2007-10-17 | 厦门大学 | Method for organochlorine pesticide photocatalytic degradation on nano titania |
| CN102962046A (en) * | 2012-03-15 | 2013-03-13 | 福建中烟工业有限责任公司 | Method for photocatalytic degradation of pesticide residues |
| CN105368587A (en) * | 2015-11-19 | 2016-03-02 | 深圳市天得一环境科技有限公司 | Touch screen water-based cleaning agent composition and use method thereof |
| CN102016463B (en) * | 2008-07-08 | 2016-04-13 | 松下电器产业株式会社 | Food storage storehouse and freezer |
| CN106118891A (en) * | 2016-06-30 | 2016-11-16 | 昆山初本电子科技有限公司 | A kind of air purifier cleanout fluid |
| CN106398896A (en) * | 2016-09-07 | 2017-02-15 | 马鞍山纽泽科技服务有限公司 | Efficient cleaning solution and preparation method thereof |
| CN109771881A (en) * | 2019-01-28 | 2019-05-21 | 刘丽丽 | A kind for the treatment of fluid and preparation method thereof reducing pesticide residue |
-
2002
- 2002-11-29 CN CNA021536015A patent/CN1504555A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342784C (en) * | 2006-03-15 | 2007-10-17 | 厦门大学 | Method for organochlorine pesticide photocatalytic degradation on nano titania |
| CN102016463B (en) * | 2008-07-08 | 2016-04-13 | 松下电器产业株式会社 | Food storage storehouse and freezer |
| CN102962046A (en) * | 2012-03-15 | 2013-03-13 | 福建中烟工业有限责任公司 | Method for photocatalytic degradation of pesticide residues |
| CN105368587A (en) * | 2015-11-19 | 2016-03-02 | 深圳市天得一环境科技有限公司 | Touch screen water-based cleaning agent composition and use method thereof |
| CN105368587B (en) * | 2015-11-19 | 2018-02-06 | 深圳市天得一环境科技有限公司 | Touch-screen water-base cleaning agent composition and its application method |
| CN106118891A (en) * | 2016-06-30 | 2016-11-16 | 昆山初本电子科技有限公司 | A kind of air purifier cleanout fluid |
| CN106398896A (en) * | 2016-09-07 | 2017-02-15 | 马鞍山纽泽科技服务有限公司 | Efficient cleaning solution and preparation method thereof |
| CN109771881A (en) * | 2019-01-28 | 2019-05-21 | 刘丽丽 | A kind for the treatment of fluid and preparation method thereof reducing pesticide residue |
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