CN102809629A - Nanometer sensitive material of dimethyl dichloroethylene phosphate ester - Google Patents
Nanometer sensitive material of dimethyl dichloroethylene phosphate ester Download PDFInfo
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- CN102809629A CN102809629A CN2012101703128A CN201210170312A CN102809629A CN 102809629 A CN102809629 A CN 102809629A CN 2012101703128 A CN2012101703128 A CN 2012101703128A CN 201210170312 A CN201210170312 A CN 201210170312A CN 102809629 A CN102809629 A CN 102809629A
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Abstract
The invention relates to nanometer sensitive material of dimethyl dichloroethylene phosphate ester, which is characterized by comprising TiO2 nano-powder, MnO2 nano-powder and Al2O3 nano-powder all doped by Pd atoms, wherein the contents of all the components are shown in percentage by weight as follows: 11-16 percent of Pd, 19-26 percent of TiO2, 20-33 percent of MnO2 and 31-45 percent of Al2O3, and the grain size range is 20-30 nm. A dimethyl dichloroethylene phosphate ester sensor made of the sensitive material provided by the invention has the advantages of wide linear scope, good selectivity, high sensitivity and the like, and trace dimethyl dichloroethylene phosphate ester can be online monitored without being affected by coexisting substances.
Description
Technical field
The present invention relates to a kind of nano sensitive material of DDVP, the TiO that especially mixes up by the Pd atom
2, MnO
2And Al
2O
3The sensitive material that nano-powder is formed belongs to field of sensing technologies.
Background technology
DDVP is commonly called as DDVP, is purposes organic phosphates Insecticidal and acaricidal agent very generally and efficiently in the agricultural production.Its pure article are colourless to amber color liquid, and boiling point is low, volatility is big and little band fragranced; Preparation is light yellow to the yellowish-brown oily liquids, in the WS, slowly decomposes, and meets alkali and decomposes quickening, to thermally-stabilised, iron is corrosive.Although it belongs to the perishability agricultural chemicals, its a large amount of uses will inevitably have a negative impact to environment, and people and animals are constituted a threat to.DDVP is the direct suppressant of cholinesterase, and the people poisons back weak point in latent period, rapid onset, the state of an illness heavily.It is faster than the inhibition of red blood cell cholinesterase to H-PchE's inhibition; In addition, DDVP also can produce and cholinesterase suppresses irrelevant another kind of toxic reaction, i.e. delayed neurotoxicity, and it can combine with neuropathy target esterase (NTE) active site, thereby suppresses its activity, the generation delayed neuropathy.In its workshop and field of employment,, myosis, see that thing is fuzzy, toxicity symptoms such as a large amount of perspirations, expiratory dyspnea often because of mistake sucks airborne volatilization medicine and causes dizziness, headache, n and V, stomachache, suffers from diarrhoea, slobbers; Severe patient, whole body have tight bundle sense, and chest has compression sense, muscle beat, move not autonomous, asophia, even tic, stupor, gatism.
The assay method of DDVP mainly contains: 1. vapor-phase chromatography (Yang Huaijin etc., microwave abstracting-vapor-phase chromatography (MAE-GC) is measured Rogor and the DDVP in the spinach, assay office, 2008, Vol.27:41-43); 2. liquid phase chromatography (Kong Na etc., the DDVP in microwave-assisted-headspace liquid-phase microextraction on-line coupling-high effective liquid chromatography for measuring environmental water sample, chromatogram, 2010, Vo.l 28, No.12:1200-1203); 3. chemoluminescence method (Bao Changli etc., the residual volume of flow injection 2 chemiluminescence determination dimethyl dichlorovinyl phosphates, 2006, Vol.44, No.4:649-651); 4. the ion mobility spectrometry method (Wang Jianfeng etc., the ion mobility spectrometry method detects DDVP and the malathion in the holy girl fruit, 2011, Vol.30, No.4:30-33); 5. catalysis photometry (Jia Yun etc., the research of catalytic Spectrophotometric Determination of Trace DDVP and application, 2005, Vol., 41, No.11:751-752) etc.These methods all need utilize analytical instrument in the laboratory, to accomplish, and can't realize on-the site analysis.
Summary of the invention
The purpose of this invention is to provide a kind of nano sensitive material to the selective response of DDVP and preparation method thereof.With the DDVP sensor that this sensitive material is made, can fast, accurately measure micro-DDVP at the scene and do not receive the interference of other concurrent.
Sensitive material of the present invention is the TiO that is mixed up by the Pd atom
2, MnO
2And Al
2O
3Nano-powder is formed, and its preparation method is:
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, use weak aqua ammonia regulator solution pH value to be 4.1-5.0; Continue to stir 5-6 hour, still aging, solution is obtained gel at 70-80 ℃ of rotary evaporation; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 580-630 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
Wherein, The potpourri of one or more of anhydride that the middle titanium salt that uses of step (1) is Titanium Nitrate, titanium phosphate, butyl titanate and titanium tetrachloride or hydrate; Manganese salt is one or more potpourri of anhydride or the hydrate of manganese acetate, manganese sulfate, manganese chloride and perchloric acid manganese, and aluminium salt is one or more potpourri of anhydride or the hydrate of aluminium nitrate, aluminium sulphate, aluminum perchlorate, aluminum phosphate, aluminum chloride, aluminum acetate, aluminium isopropoxide and aluminium secondary butylate.
When the particle diameter of nanometer powder scope that makes is 20～30nm, and each component satisfies Pd (11-16%), TiO
2(19-26%), MnO
2(20-33%) and Al
2O
3In the time of (31-45%), be used for having very high sensitivity and selectivity as the sensitive material that detects DDVP.
Embodiment
Embodiment 1
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, using weak aqua ammonia regulator solution pH value is 4.9; Continue to stir 5.1 hours, still aging, solution is obtained gel at 71 ℃ of rotary evaporations; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 582 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 20～30nm; It is carried out constituent analysis, record and consist of Pd (15.5%), TiO
2(20.1%), MnO
2(27.8%) and Al
2O
3(36.6%).
Use: with the sensitive material of this powder as the mensuration DDVP, the range of linearity 0.5～26mg/m
3, detection limit can reach 0.2mg/m
3, common concurrent does not disturb.
Embodiment 2
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, using weak aqua ammonia regulator solution pH value is 4.2; Continue to stir 5.9 hours, still aging, solution is obtained gel at 79 ℃ of rotary evaporations; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 629 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 20～30nm; It is carried out constituent analysis, record and consist of Pd (14.1%), TiO
2(25.7%), MnO
2(25.5%) and Al
2O
3(34.7%).
Use: with the sensitive material of this powder as the mensuration DDVP, the range of linearity 0.8～28mg/m
3, detection limit can reach 0.5mg/m
3, common concurrent does not disturb.
Embodiment 3
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, using weak aqua ammonia regulator solution pH value is 4.4; Continue to stir 5.3 hours, still aging, solution is obtained gel at 74 ℃ of rotary evaporations; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 607 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 20～30nm; It is carried out constituent analysis, record and consist of Pd (12.7%), TiO
2(19.5%), MnO
2(32.5%) and Al
2O
3(35.3%).
Use: with the sensitive material of this powder as the mensuration DDVP, the range of linearity 1.0～22mg/m
3, detection limit can reach 0.6mg/m
3, common concurrent does not disturb.
Embodiment 4
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, using weak aqua ammonia regulator solution pH value is 4.6; Continue to stir 5.7 hours, still aging, solution is obtained gel at 77 ℃ of rotary evaporations; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 620 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 20～30nm; It is carried out constituent analysis, record and consist of Pd (11.5%), TiO
2(23.7%), MnO
2(21.0%) and Al
2O
3(43.8%).
Use: with the sensitive material of this powder as the mensuration DDVP, the range of linearity 0.7～22mg/m
3, detection limit can reach 0.4mg/m
3, common concurrent does not disturb.
Claims (3)
1. the nano sensitive material of a DDVP is characterized in that the TiO that is mixed up by the Pd atom
2, MnO
2And Al
2O
3Nano-powder is formed, and wherein each component concentration is Pd (11-16%), TiO
2(19-26%), MnO
2(20-33%) and Al
2O
3(31-45%), its preparation method is:
(1) titanium salt, manganese salt and aluminium salt are dissolved in the WS of watery hydrochloric acid altogether, under the high-speed stirred state, add an amount of citric acid and make solution keep clear state, use weak aqua ammonia regulator solution pH value to be 4.1-5.0; Continue to stir 5-6 hour, still aging, solution is obtained gel at 70-80 ℃ of rotary evaporation; With gel infra-red drying 1 hour, after fully grinding, in high temperature box type resistance furnace, be no more than 4 ℃ speed and be warming up to 580-630 ℃ with per minute; Keep this temperature 3 hours, and obtained TiO
2, MnO
2And Al
2O
3Nano-powder;
(2) palladium bichloride being dissolved in massfraction is in 5% the aqueous hydrochloric acid solution; Under constantly stirring; The above-mentioned nano-powder that ultrasonic dispersing is crossed adds wherein, and continuation stirring and dropping massfraction are 28% hydrazine hydrate aqueous solution, mix; Directly place drying box to dry, promptly get the TiO that the Pd atom mixes up
2, MnO
2And Al
2O
3Nano-powder.
2. the nano sensitive material of a kind of DDVP according to claim 1; It is characterized in that described titanium salt is one or more a potpourri of anhydride or the hydrate of Titanium Nitrate, titanium phosphate, butyl titanate and titanium tetrachloride; Manganese salt is one or more potpourri of anhydride or the hydrate of manganese acetate, manganese sulfate, manganese chloride and perchloric acid manganese, and aluminium salt is one or more potpourri of anhydride or the hydrate of aluminium nitrate, aluminium sulphate, aluminum perchlorate, aluminum phosphate, aluminum chloride, aluminum acetate, aluminium isopropoxide and aluminium secondary butylate.
3. the nano sensitive material of a kind of DDVP according to claim 1, the particle size range that it is characterized in that described nano sensitive material is 20～30nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210170312.8A CN102809629B (en) | 2012-05-29 | 2012-05-29 | Nanometer sensitive material of dimethyl dichloroethylene phosphate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210170312.8A CN102809629B (en) | 2012-05-29 | 2012-05-29 | Nanometer sensitive material of dimethyl dichloroethylene phosphate ester |
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| Publication Number | Publication Date |
|---|---|
| CN102809629A true CN102809629A (en) | 2012-12-05 |
| CN102809629B CN102809629B (en) | 2014-12-03 |
Family
ID=47233389
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|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266990A (en) * | 1999-03-12 | 2000-09-20 | 汪土新 | Reagent for speedily detecting residual agricultural organophosphorus chemicals |
| US20100041077A1 (en) * | 2006-11-13 | 2010-02-18 | Jon Owen Nagy | Pesticide biomarker |
| CN101887057A (en) * | 2010-06-30 | 2010-11-17 | 北京联合大学生物化学工程学院 | Nano sensitive material of carbamic acid ester pesticides |
| WO2010132097A2 (en) * | 2009-05-11 | 2010-11-18 | Massachusetts Institute Of Technology | Compositions and methods for pest control |
| CN102175815A (en) * | 2010-12-07 | 2011-09-07 | 北京联合大学生物化学工程学院 | Nano-sensitive material for monitoring sulfur dioxide |
-
2012
- 2012-05-29 CN CN201210170312.8A patent/CN102809629B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266990A (en) * | 1999-03-12 | 2000-09-20 | 汪土新 | Reagent for speedily detecting residual agricultural organophosphorus chemicals |
| US20100041077A1 (en) * | 2006-11-13 | 2010-02-18 | Jon Owen Nagy | Pesticide biomarker |
| WO2010132097A2 (en) * | 2009-05-11 | 2010-11-18 | Massachusetts Institute Of Technology | Compositions and methods for pest control |
| WO2010132097A3 (en) * | 2009-05-11 | 2011-09-22 | Massachusetts Institute Of Technology | Compositions and methods for pest control |
| CN101887057A (en) * | 2010-06-30 | 2010-11-17 | 北京联合大学生物化学工程学院 | Nano sensitive material of carbamic acid ester pesticides |
| CN102175815A (en) * | 2010-12-07 | 2011-09-07 | 北京联合大学生物化学工程学院 | Nano-sensitive material for monitoring sulfur dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 孙倩: "新型纳米材料在环境与生物传感研究中的应用", 《中国优秀硕士学位论文全文数据库》 * |
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Granted publication date: 20141203 Termination date: 20160529 |