CN101251521A - Nanometer sensitive material of organic chlorine agriculture chemicals - Google Patents
Nanometer sensitive material of organic chlorine agriculture chemicals Download PDFInfo
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- CN101251521A CN101251521A CN 200810088970 CN200810088970A CN101251521A CN 101251521 A CN101251521 A CN 101251521A CN 200810088970 CN200810088970 CN 200810088970 CN 200810088970 A CN200810088970 A CN 200810088970A CN 101251521 A CN101251521 A CN 101251521A
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Abstract
The invention relates to nano sensitized materials for an organochlorine pesticide, which is characterized in that titanium salts and nickel salts which are used as raw materials undergo steps of dissolution, deposition, aging, filtering, washing, drying, grinding and calcining, etc., forming Tio2 nano powder dressed by Nio, wherein the ratio between Ti atoms and Ni atoms, the grain size of which is less than 50nm, is 100:15 to 25. A sensor of the organochlorine pesticide made of sensitized materials of the invention has the advantages of good selectivity and flexibility and being capable of detecting the content of the organochlorine pesticide in different agricultural products.
Description
Technical field
The present invention relates to a kind of sensitive material that is used to monitor organic chlorine agriculture chemicals, especially the TiO that modifies by Ni
2Type nano composite oxide sensitive material belongs to field of sensing technologies.
Background technology
Along with the development of agriculture industrialization, chemical pesticide is being brought into play more and more important effect in the production of agricultural product such as China's grain, vegetables, fruit, tealeaves and medicinal material.But, because people are to the characteristics of motion of agricultural chemicals in the nature biotechnology body, the acquisition of knowledge such as aspects such as metabolic pathway, degraded mode and residual savings is not enough, when the enjoyment chemical pesticide brings good harvest happy, has usually ignored its residual harm that brings.In the control agricultural product one of key link of persticide residue be exactly to persticide residue in the agricultural product carry out in time, analyzing and testing exactly, with the reasonable use of monitoring agricultural chemicals, prevent that the launch that residues of pesticides exceed standard from selling, guarantee agricultural product quality and safety.
Organic chlorine agriculture chemicals as benzene hexachloride and D.D.T. (dichloro-diphenyl-trichloroethane) etc., belongs to neuropoison, and it has wide spectrum and kill activity efficiently to disease and pest, is used on a large scale in early days.But because its chemical property is stable, degradation speed is slow, and is heat-resisting acidproof, residual easily, can enter human body by the effect of accumulating with food chain in the animal and plant body, and pollution of circulation can reach 20～30 years in biologic chain, causes the very big harm to health.China bans use of this type of agricultural chemicals in nineteen eighty-three, but in many agricultural product, still can detect organic chlorine agriculture chemicals at present, this is mainly owing to following two aspect reasons cause: the one, before a large amount of these type of agricultural chemicals that use residual in food chain, the 2nd, illegal farming merchant still has and uses the phenomenon that contains chloro pesticide.
The analysis and research of relevant persticide residue have a lot of reports, in the existing analytical approach, are to be main separation means with gas chromatography or liquid chromatography mostly, cooperate different detecting devices to carry out analyzing and testing again; Minority adopts separation technology such as chromatography, paper chromatography, cooperates infrared, mass spectrophotometry; Some has then adopted coupling technique, as: gas chromatography and mass spectrum, liquid chromatography and mass spectrum, Capillary Electrophoresis and mass spectrum and gas liqud chromatography and multi-stage ms coupling technique etc.These The Application of Technology have improved the qualitative ability of Detecting Pesticide and sensitivity, detectability and the detection coverage of detection greatly, but these analytical technologies are subjected to the restriction in condition, funds and place to be difficult to popularize all based on large-sized analytic instrument.
Summary of the invention
The objective of the invention is to overcome the deficiency of conventional art, nano composite oxide sensitive material of a kind of organic chlorine agriculture chemicals and preparation method thereof is provided.With the organic chlorine agriculture chemicals sensor that this sensitive material is made, can fast, accurately measure the content of the organic chlorine agriculture chemicals in the different agricultural product at the scene.
The nano composite oxide sensitive material of organic chlorine agriculture chemicals of the present invention is the TiO that is modified by NiO
2Nano-powder, its preparation method is: with can be water-soluble or ethanol in organic or inorganic titanium salt and nickel salt be that initiation material is made stable aqueous solution or ethanolic solution respectively, the solution of preparation is mixed under proper condition, and slowly generation precipitation, after ageing, filtration, washing, oven dry and grinding, make nano-powder material by high-temperature calcination.Wherein titanium salt comprises Titanium Nitrate, titanium phosphate, butyl titanate and titanium tetrachloride etc., and nickel salt comprises six water nickel chlorides, nickelous bromide, nickelous sulfate and nickel nitrate etc.
The nano composite oxide sensitive material of best organic chlorine agriculture chemicals of the present invention is with butyl titanate (C
16H
36O
4Ti) and six water nickel nitrate (Ni (NO
3)
26H
2O) make for initiation material.By the atomic ratio of Ti and Ni is that 100: 15～25 amount takes by weighing butyl titanate and six water nickel nitrates respectively, in 5%～10% aqueous hydrochloric acid solution of weight such as six water nickel nitrates are dissolved in, butyl titanate is dissolved in the 50% above ethanol water of double weight, mix after above two solution are heated to 45 ℃ respectively, keep temperature and continuous the stirring down, slowly drip the ammoniacal liquor below 30%, dripping quantity is 1/5～1/4 of a mixed liquor, rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continue to stir 1 hour, left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours, after fully grinding, in high temperature box type resistance furnace, be no more than 5 ℃ speed and be warming up to 400 ℃, and, promptly obtain nano-powder material this temperature lower calcination 4 hours with per minute.
The present invention has following remarkable advantage:
(1) utilize the alkalescent of weak aqua ammonia to come the Acidity of Aikalinity of slow regulator solution, precipitation process is slow, and particle growth is even, and gained powder body material particle size distribution range is little;
(2) prepared sensitive material has very high sensitivity to organic chlorine agriculture chemicals about 300 ℃;
Organic chlorine agriculture chemicals sensor serviceable life of (3) making with prepared sensitive material was above 200 hours.
Embodiment
Embodiment 1
By the atomic ratio of Ti and Ni is that 100: 15 amount takes by weighing butyl titanate and six water nickel nitrates respectively, and butyl titanate is dissolved in 50% ethanol water of double weight, and six water nickel nitrates are dissolved in etc. in 5% aqueous hydrochloric acid solution of weight; Mix after above two solution are heated to 45 ℃ respectively, keep temperature and constantly stir down, slowly drip 20% ammoniacal liquor, dripping quantity is 1/5 of a mixed liquor total amount, and rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continues to stir 1 hour; Left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours; After fully grinding, place high temperature box type resistance furnace to be warming up under 400 ℃, keep temperature calcining 2 hours with the speed of 2 ℃ of per minutes; Be chilled to room temperature, after careful the grinding, place high temperature box type resistance furnace to be warming up under 320 ℃ once more, keep temperature to calcine again 2 hours with the speed of 2 ℃ of per minutes.Natural cooling obtains the powder body material of particle diameter 20～35 nanometers.
Embodiment 2
By the atomic ratio of Ti and Ni is that 100: 18 amount takes by weighing butyl titanate and six water nickel chlorides respectively, and butyl titanate is dissolved in 60% ethanol water of double weight, and six water nickel chlorides are dissolved in etc. in 5% aqueous hydrochloric acid solution of weight; Mix after above two solution are heated to 45 ℃ respectively, keep temperature and constantly stir down, slowly drip 30% ammoniacal liquor, dripping quantity is 1/5 of a mixed liquor total amount, and rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continues to stir 1 hour; Left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours; After fully grinding, place high temperature box type resistance furnace to be warming up under 400 ℃, keep temperature calcining 2 hours with the speed of 3 ℃ of per minutes; Be chilled to room temperature, after careful the grinding, place high temperature box type resistance furnace to be warming up under 320 ℃ once more, keep temperature to calcine again 2 hours with the speed of 3 ℃ of per minutes.Natural cooling obtains the powder body material of particle diameter 20～40 nanometers.
Embodiment 3
By the atomic ratio of Ti and Ni is that 100: 20 amount takes by weighing butyl titanate and nickelous sulfate respectively, and butyl titanate is dissolved in 50% ethanol water of double weight, and nickelous sulfate is dissolved in etc. in 10% aqueous hydrochloric acid solution of weight; Mix after above two solution are heated to 45 ℃ respectively, keep temperature and constantly stir down, slowly drip 30% ammoniacal liquor, dripping quantity is 1/4 of a mixed liquor total amount, and rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continues to stir 1 hour; Left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours; After fully grinding, place high temperature box type resistance furnace to be warming up under 400 ℃, keep temperature calcining 2 hours with the speed of 5 ℃ of per minutes; Be chilled to room temperature, after careful the grinding, place high temperature box type resistance furnace to be warming up under 320 ℃ once more, keep temperature to calcine again 2 hours with the speed of 5 ℃ of per minutes.Natural cooling obtains the powder body material of particle diameter 20～45 nanometers.
Embodiment 4
By the atomic ratio of Ti and Ni is that 100: 22 amount takes by weighing titanium tetrachloride and six water nickel nitrates respectively, and titanium tetrachloride is dissolved in 50% ethanol water of double weight, and six water nickel nitrates are dissolved in etc. in 5% aqueous hydrochloric acid solution of weight; Mix after above two solution are heated to 45 ℃ respectively, keep temperature and constantly stir down, slowly drip 25% ammoniacal liquor, dripping quantity is 1/5 of a mixed liquor total amount, and rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continues to stir 1 hour; Left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours; After fully grinding, place high temperature box type resistance furnace to be warming up under 400 ℃, keep temperature calcining 2 hours with the speed of 3 ℃ of per minutes; Be chilled to room temperature, after careful the grinding, place high temperature box type resistance furnace to be warming up under 320 ℃ once more, keep temperature to calcine again 2 hours with the speed of 3 ℃ of per minutes.Natural cooling obtains the powder body material of particle diameter 20～40 nanometers.
Embodiment 5
By the atomic ratio of Ti and Ni is that 100: 25 amount takes by weighing Titanium Nitrate and six water nickel nitrates respectively, and Titanium Nitrate is dissolved in the aqueous solution of treble amount, and six water nickel nitrates are dissolved in etc. in 6% aqueous hydrochloric acid solution of weight; Mix after above two solution are heated to 45 ℃ respectively, keep temperature and constantly stir down, slowly drip 20% ammoniacal liquor, dripping quantity is 1/5 of a mixed liquor total amount, and rate of addition is 1 of two second, after being added dropwise to complete, is cooled to room temperature, continues to stir 1 hour; Left standstill 8 hours, will precipitate filtration under diminished pressure and use deionized water wash twice, in 115 ℃ of oven dry 2 hours; After fully grinding, place high temperature box type resistance furnace to be warming up under 400 ℃, keep temperature calcining 2 hours with the speed of 2 ℃ of per minutes; Be chilled to room temperature, after careful the grinding, place high temperature box type resistance furnace to be warming up under 320 ℃ once more, keep temperature to calcine again 2 hours with the speed of 2 ℃ of per minutes.Natural cooling obtains the powder body material of particle diameter 25～45 nanometers.
Claims (4)
1. the nano sensitive material of an organic chlorine agriculture chemicals is characterized in that the TiO that is modified by NiO
2Nano-powder is formed, and wherein the atomic ratio of Ti and Ni is 100: 15～25.
2. nano sensitive material according to claim 1 is characterized in that described nano sensitive material is that initiation material is prepared from by titanium salt and nickel salt.
3. the nano sensitive material of organic chlorine agriculture chemicals according to claim 1, the particle diameter that it is characterized in that described nano sensitive material is less than 50nm.
4. nano sensitive material according to claim 1 is characterized in that described nano sensitive material is to use in the sensor of preparation organic chlorine agriculture chemicals.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100889706A CN101251521B (en) | 2008-04-10 | 2008-04-10 | Nanometer sensitive material of organic chlorine agriculture chemicals |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100889706A CN101251521B (en) | 2008-04-10 | 2008-04-10 | Nanometer sensitive material of organic chlorine agriculture chemicals |
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| Publication Number | Publication Date |
|---|---|
| CN101251521A true CN101251521A (en) | 2008-08-27 |
| CN101251521B CN101251521B (en) | 2011-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591626C (en) * | 2008-09-08 | 2010-02-24 | 北京联合大学生物化学工程学院 | Method for degrading subaqueous organochlorine pesticide in water by photocatalysis |
| CN102807862A (en) * | 2012-05-29 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nano sensitive material for monitoring hydrogen cyanide |
| CN102809557A (en) * | 2012-01-18 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN102879521A (en) * | 2011-07-11 | 2013-01-16 | 北京联合大学生物化学工程学院 | Nano-sensitive material for monitoring hexachlorocyclohexanes |
| CN103529085A (en) * | 2013-10-04 | 2014-01-22 | 北京联合大学生物化学工程学院 | Resistance type humidity sensitive material and preparation method thereof |
-
2008
- 2008-04-10 CN CN2008100889706A patent/CN101251521B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591626C (en) * | 2008-09-08 | 2010-02-24 | 北京联合大学生物化学工程学院 | Method for degrading subaqueous organochlorine pesticide in water by photocatalysis |
| CN102879521A (en) * | 2011-07-11 | 2013-01-16 | 北京联合大学生物化学工程学院 | Nano-sensitive material for monitoring hexachlorocyclohexanes |
| CN102879521B (en) * | 2011-07-11 | 2014-10-22 | 北京联合大学生物化学工程学院 | Nano-sensitive material for monitoring hexachlorocyclohexanes |
| CN102809557A (en) * | 2012-01-18 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN102809557B (en) * | 2012-01-18 | 2015-01-28 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN102807862A (en) * | 2012-05-29 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nano sensitive material for monitoring hydrogen cyanide |
| CN103529085A (en) * | 2013-10-04 | 2014-01-22 | 北京联合大学生物化学工程学院 | Resistance type humidity sensitive material and preparation method thereof |
| CN103529085B (en) * | 2013-10-04 | 2016-07-06 | 北京联合大学生物化学工程学院 | Resistance type humidity sensitive material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101251521B (en) | 2011-02-16 |
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Granted publication date: 20110216 Termination date: 20130410 |