CN105738437A - Preparing method and application of electrochemistry parathion sensor based on metal and metal oxide co-doped nanometer composite - Google Patents

Preparing method and application of electrochemistry parathion sensor based on metal and metal oxide co-doped nanometer composite Download PDF

Info

Publication number
CN105738437A
CN105738437A CN201610101702.8A CN201610101702A CN105738437A CN 105738437 A CN105738437 A CN 105738437A CN 201610101702 A CN201610101702 A CN 201610101702A CN 105738437 A CN105738437 A CN 105738437A
Authority
CN
China
Prior art keywords
electrode
parathion
electrochemistry
solution
moo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610101702.8A
Other languages
Chinese (zh)
Other versions
CN105738437B (en
Inventor
张勇
吴丹
李燕
范大伟
魏琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201610101702.8A priority Critical patent/CN105738437B/en
Publication of CN105738437A publication Critical patent/CN105738437A/en
Application granted granted Critical
Publication of CN105738437B publication Critical patent/CN105738437B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • G01N27/301Reference electrodes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Abstract

The invention discloses a preparing method of an electrochemistry parathion sensor based on a metal and metal oxide co-doped nanometer composite, and belongs to the technical field of novel nanometer functional materials and biosensors. The preparing method comprises the steps that firstly, a novel two-dimensional manometer material Co-MoO3/TiO2@g-C3N4 is prepared, and a parathion antibody is loaded by using the good biocompatibility and the large specific area of the material; secondly, horse radish peroxidase is fixed through the cross-linking action of glutaraldehyde, in the detection process, due to the fact that horse radish peroxidase can catalyze hydrogen peroxide to generate electrochemistry signals, then the influence on the electron transmittability by the specific and quantitative combination of the antibody and an antigen is used, the current intensity is reduced correspondingly, and finally the parathion detecting electrochemistry biosensor low in cost, high in sensitivity and specificity, fast in detection and easy to prepare is obtained.

Description

A kind of based on metal and the electrochemistry pair of metal-oxide co-doped nano composite The preparation method and application of sulfur phosphorus sensor
Technical field
The present invention relates to the preparation method of a kind of electrochemistry parathion sensor.Belong to Nano-function thin films with biological Sensor technical field.
Background technology
Parathion is a kind of broad spectrum activity height poison insecticide, have tag, stomach toxicity, fumigation action, and can penetrate into plant In.Parathion to insecticide effect quickly, can be used for preventing and treating fruit tree pest insect and the wheat red mites etc. such as Cotton Gossypii, Fructus Mali pumilae, mandarin orange, pears, Fructus Persicae. In soil, parathion slightly can be migrated to deep subsoil by the eluviation of water.Parathion in soil can be by planting Thing root absorption and enter in plant.People eat by mistake this kind of plant or containing its residue plant after, parathion can pass through Digestive tract, respiratory tract and complete skin and mucosa enter human body, it may appear that Nausea and vomiting, have a headache, have loose bowels, whole body weakness nothing The preliminary symptom of poisoning such as power, is eaten for a long time or excess eats and can cause canceration.
At present, the method for detection parathion mainly has chromatography, mass spectrography etc..This type of method instrument is valuable, operation complexity, Laboratory personnel just can detect after needing professional training.Therefore, R&D costs are low, it is fast, highly sensitive, high specificity to detect Parathion sensor is significant.
Electrochemica biological sensor is widely used in facing due to advantages such as it are highly sensitive, specificity is good, easy and simple to handle The fields such as bed diagnosis, pharmaceutical analysis, environmental monitoring.The most especially more with the research of unmarked electrochemical immunosensor, it is crucial Technology be to improve the fixed amount of modified electrode antagonist and to the test signal response speed of end liquid and size.Titanium dioxide is A kind of photocatalyst material being most widely used, simultaneously because good biocompatibility, is also commonly used as electrode matrix material.By Can expose more high miller index surface in sheet-like titanium dioxide nanomaterial, have higher catalysis activity, titanium dioxide is received Rice sheet has ratio nanoparticle preferably application prospect, and the research for titanium dioxide nanoplate also receives much concern.But, dioxy The sensitivity that change titanium poorly conductive also limit the electrochemical sensor built by single titanium dioxide nano material is the highest, It is unfavorable for actual application.Semiconductor nano material is modified or is combined special nano material, on the one hand adds electrode ratio Surface area, strengthens electrodes conduct ability, and on the other hand the two can produce concerted catalysis effect, and bigger enhancing is to hydrogen peroxide Solution H2O2Catalytic response speed and current responsing signal size, be greatly improved detection sensitivity.Therefore, design, prepare height Effect, stable titanium dioxide nanoplate and trim thereof are the key technologies preparing electrochemical sensor.
Summary of the invention
It is an object of the invention to provide a kind of prepare simple, highly sensitive, detection quickly, the electrochemistry pair of high specificity The preparation method of sulfur phosphorus sensor, prepared sensor, can be used for quick, the Sensitive Detection of parathion.Based on this purpose, this First invention is prepared for the molybdenum oxide/dioxy of In-situ reaction cobalt doped in a kind of New Two Dimensional nano composite material, i.e. carbonitride Change titanium nanometer sheet Co-MoO3/TiO2@g-C3N4, utilize the good biocompatibility of this material and big specific surface area, load Upper parathion antibody, then fixes horseradish peroxidase ester by the crosslinked action of glutaraldehyde, when detecting, due to Radix Cochleariae officinalis Peroxidase can produce electrochemical signals with catalyzing hydrogen peroxide, and it is right that recycling antibody is combined with the specific quantification of antigen The impact of electron transport ability so that current intensity reduces accordingly, finally achieves employing unmarked electrochemical method detection The structure of the biosensor of parathion.
The technical solution used in the present invention is as follows:
1. the preparation side of an electrochemistry parathion sensor based on metal and metal-oxide co-doped nano composite Method, described metal and metal-oxide co-doped nano composite be the molybdenum oxide of In-situ reaction cobalt doped on carbonitride/ The two-dimensional nano composite Co-MoO of titanium dioxide nanoplate3/TiO2@g-C3N4;Described electrochemistry parathion sensor by Working electrode, Co-MoO3/TiO2@g-C3N4, parathion antibody, bovine serum albumin, glutaraldehyde, horseradish peroxidase group Become;
It is characterized in that, described preparation method includes following preparation process:
a. Co-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of electrochemistry parathion sensor;
Wherein, step a prepares Co-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdate and 0.8 ~ 1.2 mmol cobalt salt joins in 5 mL butyl titanates, stirred Cheng Zhong, is slowly added to 0.5 ~ 0.8 mL Fluohydric acid., reacts in a kettle. 18 ~ 24 hours, be cooled to room temperature at 160 ~ 200 DEG C After, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C;Secondly, 150 ~ 250 mg are taken dried Solid and the mixing of 400 mg tripolycyanamide, and grind into powder;Then, the powder of grinding is put in Muffle furnace, programming rate It is 1 ~ 3 DEG C/min, calcines 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, the most prepared Co-MoO3/TiO2@g-C3N4
Described cobalt salt is selected from one of following: cobaltous sulfate, cobaltous chloride, cobalt nitrate;
Step b prepares concretely comprising the following steps of electrochemistry parathion sensor:
(1) with glass-carbon electrode as working electrode, at the Co-MoO of electrode surface drop coating 8 ~ 12 L3/TiO2@g-C3N4Colloidal sol, room Dry under temperature;
(2) the electrode buffer solution PBS that will obtain in step (1), continues at electrode surface drop coating 8 ~ 12 L 10 The parathion antibody-solutions of g/mL, preserves in 4 DEG C of refrigerators and dries;
(3) the electrode PBS that will obtain in step (2), continuing in electrode surface drop coating 8 ~ 12 L concentration is 100 g/ The bovine serum albumin solution of mL, preserves in 4 DEG C of refrigerators and dries;
(4) the electrode PBS that will obtain in step (3), continues at the glutaraldehyde solution of electrode surface drop coating 2 ~ 4 L, and 4 DEG C refrigerator preserves and dries;
(5) the electrode PBS that will obtain in step (4), continuing in electrode surface drop coating 6 ~ 10 L concentration is 20 g/mL Horseradish peroxidase solution, 4 DEG C of refrigerators preserve and dry;
(6) the electrode PBS that will obtain in step (5), preserves in 4 DEG C of refrigerators after drying, i.e. prepares electrochemistry pair Sulfur phosphorus sensor;
Described Co-MoO3/TiO2@g-C3N4Solution is by the Co-MoO of 50 mg3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpasses In pure water, and the hydrosol prepared after ultrasonic 30 min;
Described PBS is the phosphate buffered solution of 10mmol/L, and the pH value of described phosphate buffered solution is 7.4;
Described glutaraldehyde solution be volume ratio be the glutaraldehyde water solution of 2.5%.
The application of the electrochemistry parathion sensor prepared by preparation method the most of the present invention, it is characterised in that bag Include following applying step:
A. standard solution preparation: prepare the parathion standard solution of one group of variable concentrations including blank standard specimen;
B. working electrode is modified: be work by the electrochemistry parathion sensor prepared by preparation method as claimed in claim 1 Make electrode, by the drop coating respectively of the parathion standard solution of the variable concentrations of preparation in step a to working electrode surface, 4 DEG C of ice Case preserves;
C. working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is as to electrode, with step b The working electrode composition three-electrode system modified, connects electrochemical workstation, successively adds 15 mL PBS in a cell H with 20 L 5 mol/L2O2;By the working electrode of chronoamperometry detection assembling to H2O2Response;Blank standard specimen Response current is designated as I0, the response current of the parathion standard solution containing variable concentrations is denoted as Ii, the difference of response current reduction For Δ I=I0-Ii, linear between mass concentration C of Δ I and parathion standard solution, draw Δ I-C working curve;
D. the detection of parathion: replace the parathion standard solution in step a with testing sample, according to the side in step b and c Method detects, difference DELTA I reduced according to response light signal intensity and working curve, obtains containing of parathion in testing sample Amount.
The useful achievement of the present invention
(1) electrochemistry parathion sensor of the present invention preparation is simple, easy to operate, it is achieved that quick, clever to sample Selective enumeration method quick, high, and low cost, can be applicable to portable inspectiont, has market development prospect;
(2) present invention is prepared for New Two Dimensional nano material Co-MoO first3/TiO2@g-C3N4, owing to cobalt is at molybdenum oxide/dioxy Change the growth in situ in titanium nanometer sheet and fully contact with titanium dioxide nanoplate, utilize the metal surface plasma body effect of cobalt And molybdenum oxide and the mutual promoting action both titanium dioxide, it is effectively increased semiconductor substrate electron transmission ability and catalysis Activity, although solving, titanium dioxide nanoplate specific surface area is bigger and mesoporous characteristic is applicable to electrochemical-based material, but It it is the technical problem that electro-chemical activity is the highest and current signal is unstable;Simultaneously because carbonitride g-C3N4Good electric conductivity With the characteristic of electrochemistry, add titanium dioxide nanoplate thereon fully dispersed, greatly increase electron transmission ability, Solve titanium dioxide nanoplate poorly conductive and current responsing signal is weak and be unfavorable for that the technology preparing electrochemical sensor is asked Topic, therefore, effective preparation of this material, there is important scientific meaning and using value;
(3) present invention is first by Co-MoO3/TiO2@g-C3N4It is applied in the preparation of electrochemica biological sensor, significantly improves The strength and stability of current signal, substantially increases the detection sensitivity of electrochemical sensor so that electrochemica biological passes Sensor achieves the application in real work;The application of this material, is also associated biomolecule sensor, as Optical Electro-Chemistry senses Device, Electrochemiluminescsensor sensor etc. provide Technical Reference, have the most potential use value.
Detailed description of the invention
Embodiment 1 Co-MoO3/TiO2@g-C3N4Preparation
First, take 0.6 mmol sodium molybdate and 0.8 mmol cobalt salt joins in 5 mL butyl titanates, in whipping process, slowly Add 0.5 mL Fluohydric acid., react in a kettle. at 160 DEG C 24 hours, after being cooled to room temperature, with ultra-pure water and dehydrated alcohol After centrifuge washing three times, it is vacuum dried at 50 DEG C;Secondly, take the 150 dried solids of mg and the mixing of 400 mg tripolycyanamide, And grind into powder;Then, putting in Muffle furnace by the powder of grinding, programming rate is 1 DEG C/min, calcines at 480 DEG C 5 hours;Finally, the powder after calcining is cooled to room temperature, i.e. prepares Co-MoO3/TiO2@g-C3N4
Described cobalt salt is cobaltous sulfate.
Embodiment 2 Co-MoO3/TiO2@g-C3N4Preparation
First, take 0.8 mmol sodium molybdate and 1.0 mmol cobalt salts join in 5 mL butyl titanates, in whipping process, slowly Add 0.65 mL Fluohydric acid., react in a kettle. at 180 DEG C 21 hours, after being cooled to room temperature, by ultra-pure water and anhydrous second After alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C;Secondly, take the 200 dried solids of mg and 400 mg tripolycyanamide mix Close, and grind into powder;Then, putting in Muffle furnace by the powder of grinding, programming rate is 2 DEG C/min, at 520 DEG C Calcine 2 hours;Finally, the powder after calcining is cooled to room temperature, i.e. prepares Co-MoO3/TiO2@g-C3N4
Described cobalt salt is cobaltous chloride.
Embodiment 3 Co-MoO3/TiO2@g-C3N4Preparation
First, take 1.0 mmol sodium molybdate and 1.2 mmol cobalt salts join in 5 mL butyl titanates, in whipping process, slowly Add 0.8 mL Fluohydric acid., react in a kettle. at 200 DEG C 18 hours, after being cooled to room temperature, by ultra-pure water and anhydrous second After alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C;Secondly, take the 250 dried solids of mg and 400 mg tripolycyanamide mix Close, and grind into powder;Then, putting in Muffle furnace by the powder of grinding, programming rate is 3 DEG C/min, forges at 560 DEG C Burn 0.5 hour;Finally, the powder after calcining is cooled to room temperature, i.e. prepares Co-MoO3/TiO2@g-C3N4
Described cobalt salt is cobalt nitrate.
The preparation method of embodiment 4 electrochemistry parathion sensor
(1) using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, at the Co-MoO of electrode surface drop coating 8 L3/ TiO2@g-C3N4Colloidal sol, dries under room temperature;
(2) the electrode buffer solution PBS that will obtain in step (1), continues at electrode surface drop coating 8 L 10 g/mL Parathion antibody-solutions, 4 DEG C of refrigerators preserve and dry;
(3) the electrode PBS that will obtain in step (2), continuing in electrode surface drop coating 8 L concentration is 100 g/mL Bovine serum albumin solution, 4 DEG C of refrigerators preserve and dry;
(4) the electrode PBS that will obtain in step (3), continues at the glutaraldehyde solution of electrode surface drop coating 2 L, and 4 DEG C refrigerator preserves and dries;
(5) the electrode PBS that will obtain in step (4), continuing in electrode surface drop coating 6 L concentration is 20 g/mL's Horseradish peroxidase ester solution, preserves in 4 DEG C of refrigerators and dries;
(6) the electrode PBS that will obtain in step (5), preserves in 4 DEG C of refrigerators after drying, i.e. prepares electrochemistry pair Sulfur phosphorus sensor;
Described Co-MoO3/TiO2@g-C3N4Colloidal sol is by the Co-MoO of 50 mg3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpasses In pure water, and the hydrosol prepared after ultrasonic 30 min;
Described PBS is the phosphate buffered solution of 10mmol/L, and the pH value of described phosphate buffered solution is 7.4;
Described glutaraldehyde solution be volume ratio be the glutaraldehyde water solution of 2.5%.
The preparation method of embodiment 5 electrochemistry parathion sensor
(1) using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, at the Co-of electrode surface drop coating 10 L MoO3/TiO2@g-C3N4Colloidal sol, dries under room temperature;
(2) the electrode buffer solution PBS that will obtain in step (1), continues at electrode surface drop coating 10 L 10 g/ The parathion antibody-solutions of mL, preserves in 4 DEG C of refrigerators and dries;
(3) the electrode PBS that will obtain in step (2), continuing in electrode surface drop coating 10 L concentration is 100 g/mL Bovine serum albumin solution, 4 DEG C of refrigerators preserve and dry;
(4) the electrode PBS that will obtain in step (3), continues at the glutaraldehyde solution of electrode surface drop coating 3 L, and 4 DEG C refrigerator preserves and dries;
(5) the electrode PBS that will obtain in step (4), continuing in electrode surface drop coating 8 L concentration is 20 g/mL's Horseradish peroxidase ester solution, preserves in 4 DEG C of refrigerators and dries;
(6) the electrode PBS that will obtain in step (5), preserves in 4 DEG C of refrigerators after drying, i.e. prepares electrochemistry pair Sulfur phosphorus sensor;
Described Co-MoO3/TiO2@g-C3N4Colloidal sol is by the Co-MoO of 50 mg3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpasses In pure water, and the hydrosol prepared after ultrasonic 30 min;
Described PBS is the phosphate buffered solution of 10 mmol/L, and the pH value of described phosphate buffered solution is 7.4;
Described glutaraldehyde solution be volume ratio be the glutaraldehyde water solution of 2.5%.
The preparation method of embodiment 6 electrochemistry parathion sensor
(1) using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, at the Co-of electrode surface drop coating 12 L MoO3/TiO2@g-C3N4Colloidal sol, dries under room temperature;
(2) the electrode buffer solution PBS that will obtain in step (1), continues at electrode surface drop coating 12 L 10 g/ The parathion antibody-solutions of mL, preserves in 4 DEG C of refrigerators and dries;
(3) the electrode PBS that will obtain in step (2), continuing in electrode surface drop coating 12 L concentration is 100 g/mL Bovine serum albumin solution, 4 DEG C of refrigerators preserve and dry;
(4) the electrode PBS that will obtain in step (3), continues at the glutaraldehyde solution of electrode surface drop coating 4 L, and 4 DEG C refrigerator preserves and dries;
(5) the electrode PBS that will obtain in step (4), continuing in electrode surface drop coating 10 L concentration is 20 g/mL's Horseradish peroxidase ester solution, preserves in 4 DEG C of refrigerators and dries;
(6) the electrode PBS that will obtain in step (5), preserves in 4 DEG C of refrigerators after drying, i.e. prepares electrochemistry pair Sulfur phosphorus sensor;
Described Co-MoO3/TiO2@g-C3N4Colloidal sol is by the Co-MoO of 50 mg3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpasses In pure water, and the hydrosol prepared after ultrasonic 30 min;
Described PBS is the phosphate buffered solution of 10 mmol/L, and the pH value of described phosphate buffered solution is 7.4;
Described glutaraldehyde solution be volume ratio be the glutaraldehyde water solution of 2.5%.
The electrochemistry parathion sensor of embodiment 7 embodiment 1 ~ 6 preparation, is applied to the detection of parathion, and step is such as Under:
(1) standard solution preparation: prepare the parathion standard solution of one group of variable concentrations including blank standard specimen;
(2) working electrode is modified: be work by the electrochemistry parathion sensor prepared by preparation method as claimed in claim 1 Make electrode, by the drop coating respectively of the parathion standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C Refrigerator preserves;
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is as to electrode, with step b The working electrode composition three-electrode system modified, connects electrochemical workstation, successively adds 15 mL PBS in a cell H with 20 L 5 mol/L2O2;By the working electrode of chronoamperometry detection assembling to H2O2Response;Blank standard specimen Response current is designated as I0, the response current of the parathion standard solution containing variable concentrations is denoted as Ii, the difference of response current reduction For Δ I=I0-Ii, linear between mass concentration C of Δ I and parathion standard solution, draw Δ I-C working curve; The linear detection range of parathion is: 0.009 ~ 200 ng/mL, and detection is limited to: 3.0 pg/mL;
(4) detection of parathion: replace the parathion standard solution in step (1) with testing sample, according to step (2) and (3) In method detect, according to response light signal intensity reduce difference DELTA I and working curve, obtain in testing sample sulfur The content of phosphorus.

Claims (2)

1. the preparation side of an electrochemistry parathion sensor based on metal and metal-oxide co-doped nano composite Method, described metal and metal-oxide co-doped nano composite be the molybdenum oxide of In-situ reaction cobalt doped on carbonitride/ The two-dimensional nano composite Co-MoO of titanium dioxide nanoplate3/TiO2@g-C3N4;Described electrochemistry parathion sensor by Working electrode, Co-MoO3/TiO2@g-C3N4, parathion antibody, bovine serum albumin, glutaraldehyde, horseradish peroxidase group Become;
It is characterized in that, described preparation method includes following preparation process:
a. Co-MoO3/TiO2@g-C3N4Preparation;
B. the preparation of electrochemistry parathion sensor;
Wherein, step a prepares Co-MoO3/TiO2@g-C3N4Concretely comprise the following steps:
First, take 0.6 ~ 1.0 mmol sodium molybdate and 0.8 ~ 1.2 mmol cobalt salt joins in 5 mL butyl titanates, stirred Cheng Zhong, is slowly added to 0.5 ~ 0.8 mL Fluohydric acid., reacts in a kettle. 18 ~ 24 hours, be cooled to room temperature at 160 ~ 200 DEG C After, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C;Secondly, 150 ~ 250 mg are taken dried Solid and the mixing of 400 mg tripolycyanamide, and grind into powder;Then, the powder of grinding is put in Muffle furnace, programming rate It is 1 ~ 3 DEG C/min, calcines 0.5 ~ 5 hour at 480 ~ 560 DEG C;Finally, the powder after calcining is cooled to room temperature, the most prepared Co-MoO3/TiO2@g-C3N4
Described cobalt salt is selected from one of following: cobaltous sulfate, cobaltous chloride, cobalt nitrate;
Step b prepares concretely comprising the following steps of electrochemistry parathion sensor:
(1) with glass-carbon electrode as working electrode, at the Co-MoO of electrode surface drop coating 8 ~ 12 L3/TiO2@g-C3N4Colloidal sol, room temperature Under dry;
(2) the electrode buffer solution PBS that will obtain in step (1), continues at electrode surface drop coating 8 ~ 12 L 10 The parathion antibody-solutions of g/mL, preserves in 4 DEG C of refrigerators and dries;
(3) the electrode PBS that will obtain in step (2), continuing in electrode surface drop coating 8 ~ 12 L concentration is 100 g/ The bovine serum albumin solution of mL, preserves in 4 DEG C of refrigerators and dries;
(4) the electrode PBS that will obtain in step (3), continues at the glutaraldehyde solution of electrode surface drop coating 2 ~ 4 L, and 4 DEG C refrigerator preserves and dries;
(5) the electrode PBS that will obtain in step (4), continuing in electrode surface drop coating 6 ~ 10 L concentration is 20 g/mL Horseradish peroxidase solution, 4 DEG C of refrigerators preserve and dry;
(6) the electrode PBS that will obtain in step (5), preserves in 4 DEG C of refrigerators after drying, i.e. prepares electrochemistry pair Sulfur phosphorus sensor;
Described Co-MoO3/TiO2@g-C3N4Solution is by the Co-MoO of 50 mg3/TiO2@g-C3N4Powder is dissolved in 10 mL and surpasses In pure water, and the hydrosol prepared after ultrasonic 30 min;
Described PBS is the phosphate buffered solution of 10mmol/L, and the pH value of described phosphate buffered solution is 7.4;
Described glutaraldehyde solution be volume ratio be the glutaraldehyde water solution of 2.5%.
2. the application of the electrochemistry parathion sensor prepared by preparation method as claimed in claim 1, it is characterised in that bag Include following applying step:
A. standard solution preparation: prepare the parathion standard solution of one group of variable concentrations including blank standard specimen;
B. working electrode is modified: be work by the electrochemistry parathion sensor prepared by preparation method as claimed in claim 1 Make electrode, by the drop coating respectively of the parathion standard solution of the variable concentrations of preparation in step a to working electrode surface, 4 DEG C of ice Case preserves;
C. working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is as to electrode, with step b The working electrode composition three-electrode system modified, connects electrochemical workstation, successively adds 15 mL PBS in a cell H with 20 L 5 mol/L2O2;By the working electrode of chronoamperometry detection assembling to H2O2Response;Blank standard specimen Response current is designated as I0, the response current of the parathion standard solution containing variable concentrations is denoted as Ii, the difference of response current reduction For Δ I=I0-Ii, linear between mass concentration C of Δ I and parathion standard solution, draw Δ I-C working curve;
D. the detection of parathion: replace the parathion standard solution in step a with testing sample, according to the side in step b and c Method detects, difference DELTA I reduced according to response light signal intensity and working curve, obtains containing of parathion in testing sample Amount.
CN201610101702.8A 2016-02-25 2016-02-25 A kind of preparation method and application of the electrochemistry parathion sensor based on metal and metal oxide co-doped nano composite Expired - Fee Related CN105738437B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610101702.8A CN105738437B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the electrochemistry parathion sensor based on metal and metal oxide co-doped nano composite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610101702.8A CN105738437B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the electrochemistry parathion sensor based on metal and metal oxide co-doped nano composite

Publications (2)

Publication Number Publication Date
CN105738437A true CN105738437A (en) 2016-07-06
CN105738437B CN105738437B (en) 2018-01-05

Family

ID=56249362

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610101702.8A Expired - Fee Related CN105738437B (en) 2016-02-25 2016-02-25 A kind of preparation method and application of the electrochemistry parathion sensor based on metal and metal oxide co-doped nano composite

Country Status (1)

Country Link
CN (1) CN105738437B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106908499A (en) * 2017-01-24 2017-06-30 江苏省农业科学院 Immunosensor based on composite and its method for detecting HSP90
CN108585044A (en) * 2018-05-21 2018-09-28 济南大学 The simple preparation and electro-catalysis application of a kind of Co-MoO2 nanospheres with mylikes structures
CN109254046A (en) * 2018-11-05 2019-01-22 济南大学 A kind of preparation method and application of Nitrofuran antibiotics sensor
CN109254045A (en) * 2018-11-05 2019-01-22 济南大学 A kind of preparation method and application for the cobalt-based nitride sensor detecting praziquantel
CN114720525A (en) * 2022-03-22 2022-07-08 华南农业大学 Polyvinyl alcohol/citric acid nanofiber membrane and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6445707A (en) * 1987-08-17 1989-02-20 Sumitomo Electric Industries Production of composite carbon nitride
CN103675075A (en) * 2013-11-27 2014-03-26 复旦大学 Organophosphorus detection method based on microelectrode chip
CN104777201A (en) * 2015-04-16 2015-07-15 湖北民族学院 Method for preparing electrochemical sensor for detecting parathion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6445707A (en) * 1987-08-17 1989-02-20 Sumitomo Electric Industries Production of composite carbon nitride
CN103675075A (en) * 2013-11-27 2014-03-26 复旦大学 Organophosphorus detection method based on microelectrode chip
CN104777201A (en) * 2015-04-16 2015-07-15 湖北民族学院 Method for preparing electrochemical sensor for detecting parathion

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YEPING LI,ET AL.: "Visible-light-induced blue MoO3–C3N4 composite with enhanced photocatalytic activity", 《MATERIALS RESEARCH BULLETIN》 *
傅遍红 等: "g-C3N4/TiO2复合纳米材料的制备及其光催化性能分析", 《功能材料》 *
梅长松 等: "负载金属对MoO3-TiO2光催化剂结构与催化性能的影响", 《燃料化学学报》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106908499A (en) * 2017-01-24 2017-06-30 江苏省农业科学院 Immunosensor based on composite and its method for detecting HSP90
CN106908499B (en) * 2017-01-24 2018-10-12 江苏省农业科学院 Immunosensor based on composite material and its method for detecting HSP90
CN108585044A (en) * 2018-05-21 2018-09-28 济南大学 The simple preparation and electro-catalysis application of a kind of Co-MoO2 nanospheres with mylikes structures
CN108585044B (en) * 2018-05-21 2021-01-19 济南大学 Co-MoO with mylikes structure2Simple preparation and electrocatalysis application of nanosphere
CN109254046A (en) * 2018-11-05 2019-01-22 济南大学 A kind of preparation method and application of Nitrofuran antibiotics sensor
CN109254045A (en) * 2018-11-05 2019-01-22 济南大学 A kind of preparation method and application for the cobalt-based nitride sensor detecting praziquantel
CN109254045B (en) * 2018-11-05 2021-01-12 济南大学 Cobalt-based nitride sensor for detecting praziquantel and preparation method thereof
CN114720525A (en) * 2022-03-22 2022-07-08 华南农业大学 Polyvinyl alcohol/citric acid nanofiber membrane and preparation method and application thereof
CN114720525B (en) * 2022-03-22 2024-01-05 华南农业大学 Parathion immunosensor and preparation method and application thereof

Also Published As

Publication number Publication date
CN105738437B (en) 2018-01-05

Similar Documents

Publication Publication Date Title
Xing et al. Fabrication and application of electrochemical sensor for analyzing hydrogen peroxide in food system and biological samples
CN105628758B (en) A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material
Rai et al. Implications of nanobiosensors in agriculture
CN105717181A (en) Preparation method and application of electrochemical malathion biosensor based on bi-metal in-situ composite two-dimensional nanomaterial
CN105738437A (en) Preparing method and application of electrochemistry parathion sensor based on metal and metal oxide co-doped nanometer composite
CN105572193A (en) Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite
CN105717180B (en) A kind of preparation method and application of the optical electro-chemistry aflatoxin biology sensor based on two-dimensional nano composite
CN105572108B (en) A kind of preparation method and application of electrogenerated chemiluminescence demeton sensor
CN105699645B (en) A kind of preparation method and application of electrochemistry salbutamol sensor
CN106198501B (en) A kind of preparation method for the Electrochemiluminescsensor sensor detecting aflatoxin
CN105675685B (en) A kind of preparation method and application of the electrochemistry Spanon sensor based on additive Mn two-dimensional nano composite
Vieira et al. Development of amperometric biosensors using VO2/GOx films for detection of glucose
CN105738447B (en) A kind of preparation method and application of electrochemistry chloramphenicol biology sensor
Finny et al. Cerium oxide nanoparticles for chemical and biological sensors: properties, sensing designs, and applications
CN105717178A (en) Preparation method and application of electrochemical diethylstilbestrol sensor based on titanium-dioxide-based two-dimensional composite nanomaterial
CN105738353B (en) A kind of preparation method and application of optical electro-chemistry decis sensor
CN107153088A (en) It is a kind of to be used to detect electrochemical sensor of tyrosine and its preparation method and application
CN106124589B (en) A kind of preparation method of the electrochemica biological sensor based on the building of Fe2O3 doping two-dimension nano materials
CN105717099B (en) A kind of preparation method and application of electrogenerated chemiluminescence furazolidone biology sensor
CN105738350A (en) Preparing method and application of electrochemiluminescence carbamate sensor based on cobalt-doped two-dimensional nanometer composite
Zhang et al. Recent progress on nanomaterial-based electrochemical dissolved oxygen sensors
CN106124590B (en) A kind of preparation method of electrochemistry malathion sensor
Atan et al. Novel zinc oxide nanorod and chitosan-based electrochemical glucose biosensors for glucose assay in human serum samples
CN106198672B (en) A kind of preparation method for the electrochemical sensor detecting carbamate
CN106053572A (en) Method for preparing electrochemical biphenol A sensors

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180105