CN102809554B - The nano sensitive material of biconjugate chlorphenyl trichloroethanes agricultural chemicals - Google Patents
The nano sensitive material of biconjugate chlorphenyl trichloroethanes agricultural chemicals Download PDFInfo
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- CN102809554B CN102809554B CN201110349737.0A CN201110349737A CN102809554B CN 102809554 B CN102809554 B CN 102809554B CN 201110349737 A CN201110349737 A CN 201110349737A CN 102809554 B CN102809554 B CN 102809554B
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Abstract
The present invention relates to a kind of nano sensitive material for monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals, it is characterized in that the La mixed up by Pd atom
2o
3, Fe
2o
3with NiO nano-powder composition, wherein each component concentration ranges is Pd (2-3%), La
2o
3(29-35%), Fe
2o
3(38-44%) with NiO (18-24%), particle size range is 15 ~ 35nm; The biconjugate chlorphenyl trichloroethanes agricultural chemicals sensor using sensitive material provided by the present invention to make has the wider range of linearity, good selectivity and higher sensitivity, can on-line monitoring trace biconjugate chlorphenyl trichloroethanes agricultural chemicals and not by the impact of coexisting substances.
Description
Technical field
The present invention relates to a kind of dopen Nano sensitive material for monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals, the La especially mixed up by Pd atom
2o
3, Fe
2o
3sensitive material with NiO nano-powder composition, belongs to field of sensing technologies.
Background technology
Along with the development of agriculture industrialization, chemical pesticide plays more and more important effect in the production of the agricultural product such as China's grain, veterinary antibiotics, tealeaves and medicinal material.But, because people are to the characteristics of motion of agricultural chemicals in nature biotechnology body, the acquisition of knowledge of the aspects such as such as metabolic pathway, degraded mode and residual savings is inadequate, while enjoyment chemical pesticide brings good harvest happy, usually have ignored its residual harm brought.Control one of key link of pesticide residue in agricultural products to carry out analyzing detection in time, exactly to pesticide residue in agricultural products exactly, to monitor the reasonable employment of agricultural chemicals, the launch preventing residues of pesticides from exceeding standard is sold, and guarantees agricultural product quality and safety.
Biconjugate chlorphenyl trichloroethanes (Dichlorodiphenyltrichloroethane) is again D.D.T. (dichloro-diphenyl-trichloroethane) (DDT), chemical formula (ClC
6h
4)
2cH (CCl
3), be white crystal, water insoluble, being dissolved in kerosene, can be made into emulsion, is effective pesticide.Be that 20 th Century prevent agricultural pest, alleviate the fly-borne disease harm of the mosquitos such as malaria typhoid fever and play a significant role.DDT is strangled by the diligent moral of Ou Tema to synthesize first in 1874, but the characteristic that this compound has pesticide effect is but nineteen thirty-nine just realized out by Miller.This product is almost all very effective to all insects.During World War II, the usable range of DDT obtains expansion rapidly, and exhibits one's skill to the full in the treatment of the disease such as malaria, dysentery, has given treatment to a lot of life, but also has brought the volume increase of crops.But find D.D.T. (dichloro-diphenyl-trichloroethane) very difficult degradation in the environment in the eighties of last century scientists sixties, and can accumulate in animal tallow, even in the blood of antarctic penguin, also detect D.D.T. (dichloro-diphenyl-trichloroethane), birds body includes D.D.T. (dichloro-diphenyl-trichloroethane) can be caused producing soft-shelled egg and can not hatching, and therefore bird of prey such as the U.S. national bird white-crowned sea eagle being especially in food chain climax almost becomes extinct.1962, it was cause the bird of some food meat and ichthyophagy close to the main cause of extinction that American scientist Lei Qieerkaxun suspects that in its works " silent spring " DDT enters food chain.Therefore prohibited by countries in the world gradually from D.D.T. (dichloro-diphenyl-trichloroethane) after the seventies and produce and use.DDT can accumulate for a long time in body fat, be proved and can have upset biological hormone secretion, " epidemiology " magazine of calendar year 2001 is mentioned, and scientist, by the blood sample of selective examination 24 16 to 28 years old Mexico men, confirms that in human body, the rising of DDT level can cause sperm number to reduce first.In addition, the increase of neonatal premature labor and nascent body weight also has certain to contact with DDT, and existing medical research also demonstrates it has impact to the liver function of the mankind and form, and has obvious carcinogenic performance.
DDT has higher stability and persistence, in the farmland of medication after 6 months, the evaporation of DDT still can be detected.DDT pollutes various places all over the world, from drift 1000 kilometers with dust far away with still can detect the snow-broth dissolved from the South Pole trace DDT.Generally, the concentration range of the DDT in non-agricultural district air is 1 ~ 2.36 × 10
-6ng/m
3, its concentration range of agriculture residential block is 1 ~ 22 × 10
-6ng/m
3, in the resident carrying out kill mosquito spraying, the concentration of DDT more can up to 8.5 × 10
-3mg/m
3.
The assay method of biconjugate chlorphenyl trichloroethanes agricultural chemicals mainly contains vapor-phase chromatography, liquid phase chromatography, mass spectroscopy, liquid-mass chromatography method, electrochemical process and spectrophotometric method etc., because these methods need preconcentration and suitably process ability to complete mensuration by large-sized analytic instrument more, therefore length consuming time is not easily promoted.
Summary of the invention
The object of this invention is to provide dopen Nano sensitive material of a kind of easy monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals and preparation method thereof.The sensor of the monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals made of this sensitive material, can at the scene fast, Accurate Determining micro-biconjugate chlorphenyl trichloroethanes agricultural chemicals and not by the interference of other concurrent.
Dopen Nano sensitive material of the present invention is the La mixed up by Pd atom
2o
3, Fe
2o
3with NiO nano-powder composition, its preparation method is:
(1) lanthanum salt, molysite and nickel salt are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 2.6-3.8 by ammoniacal liquor adjust ph, continue to stir 5-8 hour, still aging, solution is obtained gel at 70-85 DEG C of rotary evaporation, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 550-600 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 2-3 hour, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Wherein, the lanthanum salt used in step (1) refers to the anhydride of lanthanum nitrate, lanthanum chloride and lanthanum acetate or the potpourri of one or more of hydrate, molysite is molysite is iron chloride, ferric perchlorate, iron sulfate and the anhydride of ferric nitrate or the potpourri of one or more of hydrate, and nickel salt is the anhydride of nickel chloride, nickelous bromide, nickelous sulfate and nickel nitrate or the potpourri of one or more of hydrate.
When obtained particle diameter of nanometer powder scope is 15 ~ 35nm, and each component meets Pd (2-3%), La
2o
3(29-35%), Fe
2o
3(38-44%) time with NiO (18-24%), for there is very high sensitivity and selectivity as the sensitive material of monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals.
Embodiment
Embodiment 1
(1) lanthanum nitrate, iron sulfate and nickel chloride are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 2.8 by ammoniacal liquor adjust ph, continue stirring 6 hours, still aging, solution is obtained gel at 75 DEG C of rotary evaporations, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 560 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 2 hours, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 19 ~ 33nm; Constituent analysis is carried out to it, records and consist of 2.1%Pd, 34.1%La
2o
3, 40.7%Fe
2o
3and 23.1%NiO.
Application: using this powder as the catalytic luminescence sensitive material measuring biconjugate chlorphenyl trichloroethanes, the range of linearity 1.5 ~ 70mg/m
3, detection limit can reach 0.50mg/m
3, common agricultural chemicals concurrent does not disturb.
Embodiment 2
(1) lanthanum acetate, iron chloride, ferric perchlorate and nickel nitrate are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 3.0 by ammoniacal liquor adjust ph, continue stirring 7 hours, still aging, solution is obtained gel at 71 DEG C of rotary evaporations, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 590 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 2 hours, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 16 ~ 33nm; Constituent analysis is carried out to it, records and consist of 2.9%Pd, 32.5%La
2o
3, 43.8%Fe
2o
3and 20.8%NiO.
Application: using this powder as the catalytic luminescence sensitive material measuring biconjugate chlorphenyl trichloroethanes, the range of linearity 1.4 ~ 60mg/m
3, detection limit can reach 0.50mg/m
3, common agricultural chemicals concurrent does not disturb.
Embodiment 3
(1) lanthanum nitrate, lanthanum chloride, iron chloride, nickel chloride and nickel nitrate are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 3.7 by ammoniacal liquor adjust ph, continue stirring 6 hours, still aging, solution is obtained gel at 84 DEG C of rotary evaporations, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 580 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 3 hours, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 15 ~ 30nm; Constituent analysis is carried out to it, records and consist of 2.5%Pd, 32.3%La
2o
3, 41.5%Fe
2o
3and 23.7%NiO.
Application: using this powder as the catalytic luminescence sensitive material measuring biconjugate chlorphenyl trichloroethanes, the range of linearity 1.5 ~ 70mg/m
3, detection limit can reach 0.60mg/m
3, common agricultural chemicals concurrent does not disturb.
Embodiment 4
(1) lanthanum chloride, lanthanum acetate, ferric nitrate and nickelous sulfate are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 3.5 by ammoniacal liquor adjust ph, continue stirring 7 hours, still aging, solution is obtained gel at 78 DEG C of rotary evaporations, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 599 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 2 hours, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 21 ~ 34nm; Constituent analysis is carried out to it, records and consist of 2.7%Pd, 31.1%La
2o
3, 42.7%Fe
2o
3and 23.5%NiO.
Application: using this powder as the catalytic luminescence sensitive material measuring biconjugate chlorphenyl trichloroethanes, the range of linearity 1.2 ~ 63mg/m
3, detection limit can reach 0.40mg/m
3, common agricultural chemicals concurrent does not disturb.
Embodiment 5
(1) lanthanum chloride, ferric perchlorate, nickelous sulfate and nickel nitrate are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 2.6 by ammoniacal liquor adjust ph, continue stirring 6 hours, still aging, solution is obtained gel at 72 DEG C of rotary evaporations, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 551 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 3 hours, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
Analyze: with this powder body material of transmissioning electric mirror test, its particle size range is 17 ~ 33nm; Constituent analysis is carried out to it, records and consist of 2.6%Pd, 30.8%La
2o
3, 43.6%Fe
2o
3and 23.0%NiO.
Application: using this powder as the catalytic luminescence sensitive material measuring biconjugate chlorphenyl trichloroethanes, the range of linearity 1.0 ~ 58mg/m
3, detection limit can reach 0.40mg/m
3, common agricultural chemicals concurrent does not disturb.
Claims (2)
1. monitor a nano sensitive material for biconjugate chlorphenyl trichloroethanes agricultural chemicals, it is characterized in that the La mixed up by Pd atom
2o
3, Fe
2o
3with NiO nano-powder composition, the particle size range of nano sensitive material is 15 ~ 35nm, and wherein each component concentration is 2-3%Pd, 29-35%La
2o
3, 38-44%Fe
2o
3and 18-24%NiO, its preparation method is:
(1) lanthanum salt, molysite and nickel salt are dissolved in the aqueous solution of watery hydrochloric acid altogether, under high-speed stirred state, add appropriate citric acid makes solution keep clear state, be 2.6-3.8 by ammoniacal liquor adjust ph, continue to stir 5-8 hour, still aging, solution is obtained gel at 70-85 DEG C of rotary evaporation, by gel infra-red drying 1 hour, fully after grinding, in high temperature box type resistance furnace, be warming up to 550-600 DEG C with the speed being no more than 5 DEG C per minute, keep this temperature 2-3 hour, obtain La
2o
3, Fe
2o
3with NiO nano-powder;
(2) palladium bichloride being dissolved in massfraction is in the aqueous hydrochloric acid solution of 8%, under constantly stirring, the above-mentioned nano-powder disperseed by ultrasound wave adds wherein, continue stir and drip the hydrazine hydrate aqueous solution that massfraction is 35%, mix, directly be placed in drying box to dry, obtain the La that Pd atom mixes up
2o
3, Fe
2o
3with NiO nano-powder.
2. a kind of nano sensitive material of monitoring biconjugate chlorphenyl trichloroethanes agricultural chemicals according to claim 1, it is characterized in that described lanthanum salt refers to the anhydride of lanthanum nitrate, lanthanum chloride and lanthanum acetate or the potpourri of one or more of hydrate, molysite is iron chloride, ferric perchlorate, iron sulfate and the anhydride of ferric nitrate or the potpourri of one or more of hydrate, and nickel salt is the anhydride of nickel chloride, nickelous bromide, nickelous sulfate and nickel nitrate or the potpourri of one or more of hydrate.
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| CN100580455C (en) * | 2007-12-28 | 2010-01-13 | 北京联合大学生物化学工程学院 | Ammoniacal nanometer composite oxides sensitive material |
| CN101706485A (en) * | 2009-11-23 | 2010-05-12 | 北京联合大学生物化学工程学院 | Doped nano sensitive material for monitoring benzene |
| 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 |
-
2011
- 2011-11-08 CN CN201110349737.0A patent/CN102809554B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| CN100580455C (en) * | 2007-12-28 | 2010-01-13 | 北京联合大学生物化学工程学院 | Ammoniacal nanometer composite oxides sensitive material |
| CN101706485A (en) * | 2009-11-23 | 2010-05-12 | 北京联合大学生物化学工程学院 | Doped nano sensitive material for monitoring benzene |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 纳米复合材料催化发光法测定空气中的苯系物;周考文等;《分析试验室》;20060131;第25卷(第1期);13-16 * |
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