CN105628758B - A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material - Google Patents

A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material Download PDF

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CN105628758B
CN105628758B CN201610102027.0A CN201610102027A CN105628758B CN 105628758 B CN105628758 B CN 105628758B CN 201610102027 A CN201610102027 A CN 201610102027A CN 105628758 B CN105628758 B CN 105628758B
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parathion
electrode
chemistry
moo
tio
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CN105628758A (en
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张勇
庞雪辉
李燕
王晓东
魏琴
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University of Jinan
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements

Abstract

The invention discloses a kind of preparation method of optical electro-chemistry parathion sensor.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer light-sensitive material Mn MoO3/TiO2@g‑C3N4, good biocompatibility and big specific surface area using the material, parathion antibody in load, then alkaline phosphatase is fixed by the crosslinked action of glutaraldehyde, when being detected, because alkaline phosphatase can be catalyzed, the tricresyl phosphate sodium salt AAP of L ascorbic acid 2 is in situ to produce L ascorbic acid AA, and and then provide electron donor for Photoelectric Detection, antibody is recycled to be combined the influence to electron transport ability with the specific quantification of antigen, so that photo-current intensity accordingly reduces, it is low that cost finally has been made, high sensitivity, specificity is good, detection is quick, prepare the unmarked Photoelectrochemistrbiosensor biosensor of simple detection parathion.

Description

A kind of preparation of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material Method and application
Technical field
The present invention relates to a kind of preparation method of optical electro-chemistry parathion sensor.Belong to Nano-function thin films and life Thing sensor technical field.
Background technology
Parathion is a kind of broad spectrum activity high poison insecticide, have tag, stomach toxicity, fumigation action, and plant can be infiltrated through It is interior.Parathion is acted on insect quickly, available for fruit tree pest insects and wheat red mite etc. such as preventing and treating cotton, apple, citrus, pears, peaches. In soil, parathion can slightly be migrated by the eluviation of water to deep subsoil.Parathion in soil can pass through plant Thing root absorption and enter plant in.After people eat this kind of plant or plant containing its residue by mistake, parathion can pass through Alimentary canal, respiratory tract and complete skin and mucous membrane enter human body, it may appear that Nausea and vomiting, have a headache, have loose bowels, whole body weakness nothing The preliminary symptom of the poisonings such as power, long-term consumption or excessive eat can cause canceration.
At present, the method for detecting parathion mainly has chromatography, mass spectrography etc..Such method instrument is valuable, complex operation, Laboratory personnel could be detected after needing professional training.Therefore, R&D costs are low, detection is fast, high sensitivity, high specificity Parathion sensor is significant.
Optical electro-chemistry sensor due to high sensitivity, testing cost is low the features such as, in recent years by increasing researcher It is of interest.Optical electro-chemistry sensor is to cause electron-hole pair to be separated based on additional light source activation Electrophotosensitivmaterial material, Under suitable potential condition partially, quick transmission of the electronics on electrode, semiconductor and trim and analyte is realized, and form light Electric current.In optimal conditions, combined using biological immune, the change of analyte concentration can directly affect the size of photoelectric current, just The qualitative and quantitative analysis to analyte can be realized according to the change of photoelectric current.
Optical electro-chemistry sensor most critical technology is exactly the raising to performances such as the size of photoelectric current and stability.Titanium dioxide Titanium is a kind of photochemical catalyst and the light induced electron host material being most widely used, because sheet-like titanium dioxide nanomaterial can The more high miller index surfaces of exposure, have higher photocatalytic activity, and titanium dioxide nanoplate has than nano-particle preferably Application prospect, the research for titanium dioxide nanoplate also receive much concern.And the photoproduction electricity of single titanium dioxide nano material Son-hole is to easily compound, and so as to cause the decrease of photosignal, and titanium dioxide poorly conductive also limit by single dioxy It is universal not high to change the sensitivity of the optical electro-chemistry sensor of titanium nano material structure, is unfavorable for practical application.But in semiconductor Modification or compound special nano material in nano material, the valid density of photo-generated carrier pair can be effectively improved, improves light Photoelectric transformation efficiency, and greatly improve detection sensitivity.Therefore, design, prepare titanium dioxide nanoplate efficiently, stable and its repair Jewelry is the key technology for preparing optical electro-chemistry sensor.
The content of the invention
Prepare that simple, high sensitivity, detection be quick, optical electro-chemistry of high specificity it is an object of the invention to provide a kind of The preparation method of parathion sensor, prepared sensor, quick, Sensitive Detection available for parathion.Based on this purpose, The method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer light-sensitive material, i.e., molybdenum oxide/bis- of In-situ reaction additive Mn on carbonitride The two-dimensional nano composite Mn-MoO of TiOx nano piece3/TiO2@g-C3N4, utilize the good biocompatibility of the material With big specific surface area, parathion antibody in load, alkaline phosphatase is then fixed by the crosslinked action of glutaraldehyde, carried out During detection, because alkaline phosphatase can be catalyzed, L-AA -2- tricresyl phosphate sodium salts AAP is in situ to produce L-AA AA, And and then provide electron donor for Photoelectric Detection, recycle antibody to be combined with the specific quantification of antigen to electron transport ability Influence so that photo-current intensity accordingly reduces, and finally realizes the life using unmarked PhotoelectrochemicalMethod Method detection parathion The structure of thing sensor.
The technical solution adopted by the present invention is as follows:
1. a kind of preparation method of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material, described two Wiener rice light-sensitive material is the two-dimensional nano composite wood of molybdenum oxide/titanium dioxide nanoplate of In-situ reaction additive Mn on carbonitride Expect Mn-MoO3/TiO2@g-C3N4, described optical electro-chemistry parathion sensor is by working electrode, Mn-MoO3/TiO2@g-C3N4、 Parathion antibody, bovine serum albumin(BSA), glutaraldehyde, alkaline phosphatase composition;
Characterized in that, described preparation method includes following preparation process:
a. Mn-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of optical electro-chemistry parathion sensor;
Wherein, step a prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdates and 0.8 ~ 1.2 mmol manganese salts to be added in 5 mL butyl titanates, stir During mixing, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, reacts 18 ~ 24 hours, is cooled in a kettle at 160 ~ 200 DEG C After room temperature, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, 150 ~ 250 mg are taken to dry Solid afterwards mixes with 400 mg melamines, and grind into powder;Then, the powder of grinding is put into Muffle furnace, heated up Speed is 1 ~ 3 DEG C/min, is calcined 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, i.e., Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is selected from one of following:Manganese sulfate, manganese chloride, manganese nitrate;
Step b prepares concretely comprising the following steps for optical electro-chemistry parathion sensor:
(1)Using ITO electro-conductive glass as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 Mn-MoO3/TiO2@g-C3N4 Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L of electrode surface drop coating 8 ~ 12 10 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 to continue in the μ L concentration of electrode surface drop coating 8 ~ 12 μ g/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 ~ 4 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ to continue in the μ L concentration of electrode surface drop coating 6 ~ 10 G/mL alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the optical electro-chemistry parathion sensor prepared by preparation method of the present invention, it is characterised in that Including following applying step:
A. standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
B. working electrode is modified:By the optical electro-chemistry parathion sensor prepared by preparation method as described in the present invention For working electrode, the parathion standard liquid for the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C Preserved in refrigerator;
C. working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step The working electrode composition three-electrode system that rapid b has been modified, is connected on optical electro-chemistry detection device;Successively add in a cell Enter 15mL pH=5.4 Tris-HCl cushioning liquid and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP it is molten Liquid;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, drawing Curve;
D. the detection of parathion:The parathion standard liquid in step a is replaced with testing sample, according in step b and c Method detected, according to the photocurrent values and working curve of gained, obtain the content of parathion in testing sample.
The useful achievement of the present invention
(1)Optical electro-chemistry parathion sensor of the present invention is prepared simply, easy to operate, is realized to the fast of sample Fast, sensitive, high selectivity detection, and cost is low, can be applied to portable inspectiont, has market development prospect;
(2)The present invention is prepared for New Two Dimensional light-sensitive material Mn-MoO first3/TiO2@g-C3N4, due to manganese molybdenum oxide/ Growth in situ on titanium dioxide nanoplate and fully contacted with titanium dioxide nanoplate, utilize the metal surface plasma body of manganese The mutual promoting action of both effect and molybdenum oxide and titanium dioxide, effectively prevents the compound of photo-generate electron-hole pair, solves Although titanium dioxide nanoplate photocatalysis effect of having determined is good, photoelectric current produces less technical problem;Simultaneously because nitridation Carbon g-C3N4Good electric conductivity and molybdenum oxide/titanium dioxide nanoplate it is fully dispersed thereon, greatly increase oxidation The photocatalytic activity of molybdenum/titanium dioxide nanoplate and solve molybdenum oxide/titanium dioxide nanoplate poorly conductive and be unfavorable for making The technical problem of standby optical electro-chemistry sensor, therefore, effective preparation of the material, there is important scientific meaning and using valency Value;
(3)The present invention is first by Mn-MoO3/TiO2@g-C3N4Applied in the preparation of Photoelectrochemistrbiosensor biosensor, show The valid density for improving photo-generated carrier is write, substantially increases the detection sensitivity of optical electro-chemistry sensor so that photoelectrochemical Biosensors realize the application in real work;The application of the material, also it is associated biomolecule sensor, such as electroluminescentization Learn luminescence sensor, electrochemical sensor etc. and provide Technical Reference, there is extensive potential use value.
Embodiment
The Mn-MoO of embodiment 13/TiO2@g-C3N4Preparation
First, 0.6 mmol sodium molybdates and 0.8 mmol manganese salts is taken to be added in 5 mL butyl titanates, in whipping process, 0.5 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 160 DEG C 24 hours, after being cooled to room temperature, with ultra-pure water and anhydrous Ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 150 mg are taken to be mixed with 400 mg melamines Close, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 1 DEG C/min, at 480 DEG C Calcining 5 hours;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese sulfate.
The Mn-MoO of embodiment 23/TiO2@g-C3N4Preparation
First, 0.8 mmol sodium molybdates and 1.0 mmol manganese salts are taken to be added in 5 mL butyl titanates, in whipping process, 0.65 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 180 DEG C 21 hours, after being cooled to room temperature, with ultra-pure water and nothing Water-ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 200 mg and 400 mg melamines are taken Mixing, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 2 DEG C/min, at 520 DEG C Lower calcining 2 hours;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese chloride.
The Mn-MoO of embodiment 33/TiO2@g-C3N4Preparation
First, 1.0 mmol sodium molybdates and 1.2 mmol manganese salts are taken to be added in 5 mL butyl titanates, in whipping process, 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 200 DEG C 18 hours, after being cooled to room temperature, with ultra-pure water and nothing Water-ethanol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, the dried solids of 250 mg and 400 mg melamines are taken Mixing, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate is 3 DEG C/min, at 560 DEG C Calcining 0.5 hour;Finally, the powder after calcining is cooled to room temperature, that is, Mn-MoO is made3/TiO2@g-C3N4
Described manganese salt is manganese nitrate.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 4
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 8 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ of 8 μ L of electrode surface drop coating 10 G/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 8 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 6 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 5
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 10 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 10 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 10 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 3 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the optical electro-chemistry parathion sensor of embodiment 6
(1)Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 12 Mn-MoO3/TiO2@g-C3N4Colloidal sol, dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 12 μ g/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 12 G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 4 is molten Liquid, preserve in 4 DEG C of refrigerators and dry;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 10 ML alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, photoelectricity be made Chemical parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 In mL ultra-pure waters, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
Optical electro-chemistry parathion sensor prepared by the embodiment 1 ~ 6 of embodiment 7, applied to the detection of parathion, step is such as Under:
(1)Standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
(2)Working electrode is modified:By the optical electro-chemistry parathion sensor prepared by preparation method as described in the present invention For working electrode, by step(1)The parathion standard liquids of the various concentrations of middle preparation distinguishes drop coating to working electrode surface, and 4 Preserved in DEG C refrigerator;
(3)Working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step Suddenly(2)The working electrode composition three-electrode system modified, is connected on optical electro-chemistry detection device;In a cell successively Add the Tris-HCl cushioning liquid of 15mL pH=5.4 and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP Solution;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, work is drawn Make curve;The linear detection range of parathion is:0.003 ~ 200 ng/mL, detection are limited to:1.0 pg/mL;
(4)Actual sample detects:Step is replaced with testing sample(1)In parathion standard liquid, according to step(2)With (3)In method detected, according to the photocurrent values and working curve of gained, obtain the content of parathion in testing sample.

Claims (2)

1. a kind of preparation method of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material, described two-dimensional nano Light-sensitive material is the two-dimensional nano composite Mn- of molybdenum oxide/titanium dioxide nanoplate of In-situ reaction additive Mn on carbonitride MoO3/TiO2@g-C3N4, described optical electro-chemistry parathion sensor is by working electrode, Mn-MoO3/TiO2@g-C3N4, parathion Antibody, bovine serum albumin(BSA), glutaraldehyde, alkaline phosphatase composition;
Characterized in that, described preparation method includes following preparation process:
a. Mn-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of optical electro-chemistry parathion sensor;
Wherein, step a prepares Mn-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, 0.6 ~ 1.0 mmol sodium molybdates and 0.8 ~ 1.2 mmol manganese salts is taken to be added in 5 mL butyl titanates, it is stirred Cheng Zhong, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 160 ~ 200 DEG C 18 ~ 24 hours, is cooled to room temperature Afterwards, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be dried in vacuo at 50 DEG C;Secondly, take 150 ~ 250 mg dried Solid mixes with 400 mg melamines, and grind into powder;Then, the powder of grinding is put into Muffle furnace, programming rate For 1 ~ 3 DEG C/min, calcined 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, that is, be made Mn-MoO3/TiO2@g-C3N4
Described manganese salt is selected from one of following:Manganese sulfate, manganese chloride, manganese nitrate;
Step b prepares concretely comprising the following steps for optical electro-chemistry parathion sensor:
(1)Using ITO electro-conductive glass as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 Mn-MoO3/TiO2@g-C3N4Colloidal sol, Dry at room temperature;
(2)By step(1)In obtained electrode cushioning liquid PBS, continue in the μ of 8 ~ 12 μ L of electrode surface drop coating 10 G/mL parathion antibody-solutions, preserve in 4 DEG C of refrigerators and dry;
(3)By step(2)In obtained electrode PBS, it is 100 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ~ 12 ML bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry;
(4)By step(3)In obtained electrode PBS, continue the glutaraldehyde solution in the μ L of electrode surface drop coating 2 ~ 4,4 Preserve and dry in DEG C refrigerator;
(5)By step(4)In obtained electrode PBS, it is 20 μ g/mL to continue in the μ L concentration of electrode surface drop coating 6 ~ 10 Alkaline phosphatase enzyme solutions, preserve in 4 DEG C of refrigerators and dry;
(6)By step(5)In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, optical electro-chemistry be made Parathion sensor;
Described Mn-MoO3/TiO2@g-C3N4Colloidal sol is by 50 mg Mn-MoO3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpassed In pure water, and the obtained hydrosol after 30 min of ultrasound;
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4;
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the optical electro-chemistry parathion sensor prepared by preparation method as claimed in claim 1, it is characterised in that Including following applying step:
A. standard liquid is prepared:Prepare the parathion standard liquid of one group of various concentrations including blank standard specimen;
B. working electrode is modified:It is by the optical electro-chemistry parathion sensor prepared by preparation method as claimed in claim 1 Working electrode, the parathion standard liquids of the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C Preserved in refrigerator;
C. working curve is drawn:Using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step b institutes The working electrode composition three-electrode system modified, is connected on optical electro-chemistry detection device;Successively add in a cell Tris-HCl the cushioning liquid of 15mL pH=5.4 and the mmol/L of 5 mL 10 L-AA -2- tricresyl phosphate sodium salts AAP are molten Liquid;Using i-t means of testing, according to the relation between the photocurrent values of gained and parathion concentration of standard solution, drawing Curve;
D. the detection of parathion:The parathion standard liquid in step a is replaced with testing sample, according to the side in step b and c Method is detected, and according to the photocurrent values and working curve of gained, obtains the content of parathion in testing sample.
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