CN106970134A - A kind of organophosphorus reagent analyzing detecting method based on mesopore metal oxide - Google Patents
A kind of organophosphorus reagent analyzing detecting method based on mesopore metal oxide Download PDFInfo
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Abstract
The invention belongs to technical field of analysis and detection, specially a kind of organophosphorus reagent analyzing detecting method based on mesopore metal oxide.The invention belongs to using mesopore metal oxide as substrate, analysis is used for quickly detecting to organophosphorus reagent.The present invention is first by template, and metal oxide precursor is dissolved in ethanol system, utilizes the synthesising mesoporous metal oxide materials of the method for solvent evaporation induced self-assembly；Mesoporous metallic oxide material modification is arrived by glassy carbon electrode surface by drop-coating again, micro organophosphorus reagent in solution detected using differential pulse voltammetry.The present invention realizes the quick detection to micro organophosphorus reagent in solution by the organophosphor detection architecture of foundation, and test limit can reach 0.5 nanograms/milliliter, is that a kind of sensitivity is high, analyzing detecting method easy to operate.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to organophosphorus reagent analyzing detecting method.
Background technology
Metal oxide particularly transition metal oxide（Including metal composite oxide）It is used as the important function of a class
Material such as is widely used in being catalyzed, sensed at the field.The high porosity that wherein ordered mesoporous metal oxide has, compares greatly table
Area, aperture is adjustable and in single distribution, the features such as good hydrothermal stability, overcomes the deficiency of conventional metal oxides,
In light, electricity, magnetic is catalyzed, and all there is tempting application prospect in the field such as sensing（Hu J S, Zhong L S, Song W G,
et al. Adv. Mater., 2008, 20, 2977-2982）.
Solvent evaporation induced self-assembly method is incorporated into synthesising mesoporous metal oxide first from Yang in 1998 etc., it is real
Show and mesopore metal oxide is prepared in organic solvent system, so as to alleviate the hydrolysis of metal material resource to a certain extent and poly-
The problem such as close, Yang etc. has synthesized a series of mesoporous metal of good hydrothermal stabilities using triblock copolymer as template direction agent
Oxide（Titanium dioxide, zirconium dioxide, alundum (Al2O3), tungsten oxide etc.）（Yang P D, Zhao D Y, Margolese D
I, et al. Nature, 1998, 396, 152-155）.These metal oxides are with non-ionic block copolymer
（P123, F127 etc.）For structure directing agent, using inorganic salts as hydrolysis presoma in non-aqueous solution, polymer-metal oxygen is formed
Compound framework, removes eventually through roasting and specific surface area is made after directed agents greatly, pore passage structure rule and good Jie of heat endurance
Mesoporous metal oxide.
In numerous mesopore metal oxides, zirconium oxide is a kind of material for being widely used and being readily synthesized, and to having
Machine phosphorus reagent has strong affinity effect.So the present invention passes through electrochemical analysis emphatically using mesoporous zircite as substrate
Method is used for quickly detecting to the content of organophosphorus reagent in solution.Mesoporous zircite not only has mesoporous material specific surface area
Greatly, the characteristics of aperture is homogeneous, and there is acid and basic surface center simultaneously, it is P-type semiconductor again, it is easy to produce oxygen empty
Cave, there is special compatibility to oxy radical, thus with good absorption property, is carried in detection of organic phosphorus pesticide and catalyst
Have broad application prospects in terms of body.Meanwhile, the present invention also extends to preparation and the organophosphorus reagent of other metal oxides
Detection, such as meso-porous alumina, meso-porous titanium oxide, mesoporous tungsten oxide etc..
The content of the invention
Present invention aims at propose a kind of quick, accurate, stable organophosphorus reagent analyzing detecting method.
Organophosphorus reagent analyzing detecting method proposed by the present invention, it is nanocrystalline for detection substrate with mesopore metal oxide,
Wherein main use has the zirconium oxide nano crystal of strong affinity to organophosphorous groups for base material, and using electrochemical process come
Realize the quick analysis detection of organophosphor.
Organophosphorus reagent detection method proposed by the present invention, it is nanocrystalline for detection substrate with mesopore metal oxide, it is organic
Phosphorus detection uses voltammetry, concretely comprises the following steps：
（1）Mesopore metal oxide manocrystalline powders are taken, the turbid liquid of 1-2 mg/mls is made；
（2）Take above-mentioned 10-20 microlitres of turbid drop to be coated onto glassy carbon electrode surface, dry, 3-5 microlitres of concentration is then dripped again is
0.5%-1% nafion solution, continues to dry；
（3）Take a certain amount of phosphate buffer solution to be put in beaker, electrode be placed in cushioning liquid, first sweep blank cycle volt-ampere,
Activated electrode is to stabilization, then sweeps blank differential pulse voltammetry, to be used as contrast；
（4）Then, a certain amount of organophosphorus reagent is injected into above-mentioned solution, the solution of concentration, passes through current method needed for being made into
Adsorb organophosphor 180-300 seconds, be measured with cyclic voltammetry or differential pulse voltammetry.
In the present invention, described mesoporous metallic oxide material is mainly mesoporous zircite, it would however also be possible to employ mesoporous oxidation
Aluminium, meso-porous titanium oxide, mesoporous tungsten oxide etc. are a variety of.
In the present invention, the mesopore oxide can be prepared using the method for solvent evaporation induced self-assembly, be concretely comprised the following steps：
Mesopore oxide source, template, solvent, water are mixed into stirring reaction first；Then paving disk volatilization in atmosphere；Then
Plate is put into baking oven curing process, sample is put into Muffle furnace and is calcined by last scraping disc.
In the present invention, the mesopore oxide source can be zirconium source, silicon source, titanium source or tungsten source, and used zirconium source is chlorination
Zirconium, chlorine oxygen zirconium, acetylacetone,2,4-pentanedione zirconium or zirconium nitrate etc.；Used silicon source is aluminium acetylacetonate or aluminium isopropoxide etc.；It is used
Titanium source is tetrabutyl titanate, isopropyl titanate or titanium tetrachloride etc.；Used tungsten source is tungsten chloride etc..
In the present invention, it is F127, P123, PEO-b-PS or PS-b-P4VP etc. to use template.
In the present invention, the mass ratio of the mesopore oxide source and template is 3:1~1:1.
In the present invention, solvent preferred alcohol is used.
In the present invention, prepare during zirconium oxide, the stirring reaction time is 1.5-3 h, and the paving disk volatilization time is 5-10
Min, curing oven temperature is 40-100 DEG C, and hardening time is 18-30h, and roasting crystallization temperature is 350-500 DEG C, roasting time
For 2-4h；Prepare during titanium oxide, the stirring reaction time is 2-6h, spread disk volatilization time 12-24h, curing oven temperature is
40-100 DEG C, hardening time is 18-30h, and sintering temperature is 350-450 DEG C, and roasting time is 15min-2h；Prepare aluminum oxide mistake
Cheng Zhong, the stirring reaction time is 6-12h, paving disk volatilization time 2-4h, and curing oven temperature is 40-100 DEG C, and hardening time is
18-30h, sintering temperature is 600-900 DEG C, and roasting time is 2-3h.Prepare during tungsten oxide, the stirring reaction time is 1-
2h, the paving disk volatilization time is 4-6h, and curing oven temperature is 40-100 DEG C, and hardening time is 18-30h, and sintering temperature is 350-
450 DEG C, roasting time is 2-3h.
The nanocrystalline feature of mesopore oxide prepared by the present invention is characterized with the following method：
Powder x-ray diffraction (XRD).This X ray diffracting spectrum is compared with standard PDF, and the product that the method is obtained is single
Crystallize complete crystal.
SEM（SEM）And transmission electron microscope（TEM）.Its rule can intuitively be judged very much
Crystal formation pattern and size.
The machine phosphorus reagent determined in the present invention can be parathion-methyl, the organophosphor containing nitryl group such as methyl paraoxon
Reagent.
The method that organophosphor is detected in the present invention is cyclic voltammetry, differential pulse voltammetry.
The present invention is compared to traditional gas phase, liquid chromatography, and mass spectrography is detected and other organic phosphorus detection methods,
Operation is simple, spends cost lower, and detects sensitiveer, and actually detected concentration low can reach 1ng/ml, far below 3ng/ml（M.
Wang, ZY. Li, Sens. Actuators, B. 133 (2008) 607-612）, 5ng/ml（GD, Liu. YH,
Lin. Anal. Chem. 2005, 77, 5894-5901）Deng.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of prepared ordered mesoporous zirconia.Top is divided into the X-ray of zirconia material
Diffraction pattern, bottom is divided into the standard PDF cards of the tetragonal phase zirconium oxide of standard, and contrast can prove the zirconium oxide that the present invention is obtained
It is the zirconium oxide of tetragonal structure.
Fig. 2 is the cyclic voltammetric collection of illustrative plates that organophosphor is tested.Wherein, inner ring smoothed curve is free of organophosphorus reagent for detection
There is the curve of the symmetrical peak of a pair of protrusions blank cycle voltammogram, outer ring to detect that a certain amount of organophosphorus reagent is deposited near zero volt
Cyclic voltammetric collection of illustrative plates in the case of, contrast blank cycle voltammogram is it is obvious that detect a certain amount of organophosphorus reagent
Cyclic voltammogram, which has near 0 volt near a pair of obvious redox character peaks, -0.7 volt, has a reduction characteristic peak to occur,
Exactly correspond to the redox reversible transformation between nitryl group and oxyammonia group in organophosphorus reagent.
Fig. 3 is the differential pulse voltammetry collection of illustrative plates that organophosphor is detected.Wherein, it is selected be the reduction peak near zero volt inspection
Survey.The concentration of the organophosphorus reagent from top to bottom detected respectively 1ng/ml, 2ng/ml, 5ng/ml, 10ng/ml, 20ng/ml,
40ng/ml, 80ng/ml.Find that good linear relationship is presented in the range of 1-80ng/ml by linear analogue result.
Fig. 4 schemes for the SEM and TEM of zirconia material.Wherein, a, b are SEM phenograms, it can be seen that hole is significantly in have
Sequence is arranged, c, and d is TEM phenograms, it will also be seen that the duct of ordered arrangement, and can be evaluated whether what is portalled from figure c
Size is 6-7nm.Also far it is satisfied with the absorption and transmission of organophosphor molecule in such duct.
Embodiment
With when result such as following table
。
Claims (7)
1. a kind of organophosphorus reagent analyzing detecting method based on mesopore metal oxide, it is characterised in that concretely comprise the following steps：
（1）Mesopore metal oxide manocrystalline powders are taken, the turbid liquid of 1-2 mg/mls is made；
（2）Take above-mentioned 10-20 microlitres of turbid drop to be coated onto glassy carbon electrode surface, dry, 3-5 microlitres of concentration is then dripped again is
0.5%-1% nafion solution, continues to dry；
（3）Take a certain amount of phosphate buffer solution to be put in beaker, electrode be placed in cushioning liquid, first sweep blank cycle volt-ampere,
Activated electrode is to stabilization, then sweeps blank differential pulse voltammetry, to be used as contrast；
（4）Then, organophosphorus reagent is injected into above-mentioned solution, the solution of concentration, adsorbs organic by current method needed for being made into
Phosphorus 180-300 seconds, is measured with cyclic voltammetry or differential pulse voltammetry.
2. organophosphorus reagent analyzing detecting method according to claim 1, it is characterised in that the mesopore oxide is used
Prepared by the method for solvent evaporation induced self-assembly, concretely comprise the following steps：Mesopore oxide source, template, solvent, water are mixed first
Together, stirring reaction；Then paving disk volatilization in atmosphere；Plate is then put into baking oven curing process, last scraping disc will
Sample is put into Muffle furnace roasting.
3. organophosphorus reagent analyzing detecting method according to claim 2, it is characterised in that the mesopore oxide source is
Zirconium source, silicon source, titanium source or tungsten source.
4. organophosphorus reagent analyzing detecting method according to claim 3, it is characterised in that used zirconium source is chlorination
Zirconium, chlorine oxygen zirconium, acetylacetone,2,4-pentanedione zirconium or zirconium nitrate；Used silicon source is aluminium acetylacetonate or aluminium isopropoxide；Used titanium source
For tetrabutyl titanate, isopropyl titanate or titanium tetrachloride；Used tungsten source is tungsten chloride.
5. the organophosphorus reagent analyzing detecting method according to claim 2,3 or 4, it is characterised in that use template
For F127, P123, PEO-b-PS or PS-b-P4VP.
6. organophosphorus reagent analyzing detecting method according to claim 5, it is characterised in that the mesopore oxide source with
The mass ratio of template is 3:1~1:1.
7. organophosphorus reagent analyzing detecting method according to claim 5, it is characterised in that：
Prepare during zirconium oxide, the stirring reaction time is 1.5-3 h, and the paving disk volatilization time is 5-10 min, curing oven temperature
Spend for 40-100 DEG C, hardening time is 18-30h, roasting crystallization temperature is 350-500 DEG C, and roasting time is 2-4h；
Prepare during titanium oxide, the stirring reaction time is 2-6h, paving disk volatilization time 12-24h, and curing oven temperature is 40-
100 DEG C, hardening time is 18-30h, and sintering temperature is 350-450 DEG C, and roasting time is 15min-2h；
Prepare in alumina process, the stirring reaction time is 6-12h, paving disk volatilization time 2-4h, and curing oven temperature is 40-
100 DEG C, hardening time is 18-30h, and sintering temperature is 600-900 DEG C, and roasting time is 2-3h；
Prepare during tungsten oxide, the stirring reaction time is 1-2h, the paving disk volatilization time is 4-6h, and curing oven temperature is 40-
100 DEG C, hardening time is 18-30h, and sintering temperature is 350 ~ 450 DEG C, and roasting time is 2-3h.
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| CN108490062A (en) * | 2018-03-19 | 2018-09-04 | 广东华晟安全职业评价有限公司 | The detection method of phosphorus and its compound in a kind of detection workplace air |
| CN109663562A (en) * | 2019-01-21 | 2019-04-23 | 中国科学院上海微系统与信息技术研究所 | A kind of control method of Metaporous silicon dioxide material to organic phosphorus adsorption rate |
| CN115926180A (en) * | 2022-11-08 | 2023-04-07 | 复旦大学 | Adjustable hierarchical pore metal organic framework material and preparation method and application thereof |
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| CN108490062A (en) * | 2018-03-19 | 2018-09-04 | 广东华晟安全职业评价有限公司 | The detection method of phosphorus and its compound in a kind of detection workplace air |
| CN109663562A (en) * | 2019-01-21 | 2019-04-23 | 中国科学院上海微系统与信息技术研究所 | A kind of control method of Metaporous silicon dioxide material to organic phosphorus adsorption rate |
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| CN115926180A (en) * | 2022-11-08 | 2023-04-07 | 复旦大学 | Adjustable hierarchical pore metal organic framework material and preparation method and application thereof |
| CN115926180B (en) * | 2022-11-08 | 2023-11-07 | 复旦大学 | Metal organic framework material with adjustable hierarchical holes and preparation method and application thereof |
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Application publication date: 20170721 |