CN106124588B - A kind of preparation method of the electrochemistry nonyl phenol sensor based on titania-doped/molybdenum disulfide composite material - Google Patents

A kind of preparation method of the electrochemistry nonyl phenol sensor based on titania-doped/molybdenum disulfide composite material Download PDF

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CN106124588B
CN106124588B CN201610521133.2A CN201610521133A CN106124588B CN 106124588 B CN106124588 B CN 106124588B CN 201610521133 A CN201610521133 A CN 201610521133A CN 106124588 B CN106124588 B CN 106124588B
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nonyl phenol
molybdenum disulfide
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张勇
杜斌
马洪敏
吴丹
范大伟
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University of Jinan
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Abstract

The invention discloses a kind of preparation methods of electrochemica biological sensor.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nano-electrode materials --- titania-doped/molybdenum disulfide composite material Cu-TiO2/MoS2That is the two-dimensional nano composite material of copper-doped titanium dioxide nano square In-situ reaction molybdenum disulfide, good biocompatibility and big specific surface area using the material, nonyl phenol antibody in load, when being detected, since copper-doped titanium dioxide can be with catalyzing hydrogen peroxide in-situ preparation O2, electrochemical signals are generated, recycle antibody in conjunction with the specific quantification of antigen to the influence of electron transport ability, so that current strength accordingly reduces, finally realize the building of the biosensor using unmarked electrochemical method detection nonyl phenol.

Description

A kind of electrochemistry nonyl phenol based on titania-doped/molybdenum disulfide composite material The preparation method of sensor
Technical field
The present invention relates to a kind of preparation methods of electrochemica biological sensor.Belong to Nano-function thin films and biology passes Sensor technical field.
Background technique
After environmental estrogens refer to that one kind enters body, synthesis, release, fortune with normal endocrine substance in interfering bodies The processes such as defeated, combination, metabolism, activate or inhibit the function of endocrine system, maintain organism stability and regulation to make to destroy Compound, environmental estrogens are many kinds of, including artificial-synthetic compound and natural plant estrogen, are distributed widely in certainly In right boundary.Nonyl phenol is a type bisphenols synthetic estrogen.Currently, the method for detection nonyl phenol mainly has chromatography, matter Spectrometry etc..Such method instrument is valuable, complicated for operation, and laboratory personnel just can be carried out detection after needing professional training.Therefore, it researches and develops It is at low cost, detection is fast, high sensitivity, high specificity nonyl phenol sensor is of great significance.
Electrochemica biological sensor due to its high sensitivity, specificity it is good, easy to operate the advantages that be widely used in facing The fields such as bed diagnosis, Pharmaceutical Analysis, environmental monitoring.More, key is wherein studied with unmarked electrochemical immunosensor especially Technology be to improve modified electrode to the fixed amount of antibody and to the signal response speed and size of test bottom liquid.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 More high miller index surfaces can be exposed in sheet-like titanium dioxide nanomaterial, there is higher catalytic activity, titanium dioxide is received Rice piece has application prospect preferably than nanoparticle, and the research of titanium dioxide nanoplate is also concerned.But dioxy The sensitivity that change titanium poorly conductive also limits the electrochemical sensor constructed by single titanium dioxide nano material is not generally high, It is unfavorable for practical application.Modification or compound special nano material, on the one hand increase electrode ratio on semiconductor nano material Surface area enhances 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, greatly improve detection sensitivity.Therefore, it designs, prepare height Effect, stable titanium dioxide nanoplate and its modifier are the key technologies for preparing electrochemical sensor.
Molybdenum disulfide (chemical formula MoS2) nano material, there is two-dimensional layered structure, be most widely used solid profit One of lubrication prescription.Its sheet two-dimension nano materials after removing, is the semiconductor nano material haveing excellent performance, in addition to big ratio Surface area, can be used as the carrier of catalyst and biological antibody, improve load capacity, while also have as co-catalyst excellent Electron transmission performance.
Currently, most of synthesizing mean is all after being separately synthesized, then catalyst and carrier progress is compound, process is numerous Trivial, yield is not high.Therefore, have for two dimensional nano electrodes material of the In-situ reaction preparation with excellent chemical property extensive Application prospect and important scientific meaning.
Summary of the invention
The purpose of the present invention is to provide it is a kind of prepare simple, high sensitivity, detection quickly, the electrochemical student of high specificity The preparation method of object sensor, prepared sensor can be used for quick, the Sensitive Detection of nonyl phenol.Based on this purpose, this hair It is bright to be prepared for a kind of New Two Dimensional nano-electrode material first --- titania-doped/molybdenum disulfide composite material Cu-TiO2/ MoS2, i.e. the two-dimensional nano composite material of copper-doped titanium dioxide nano square In-situ reaction molybdenum disulfide utilizes the material Good biocompatibility and big specific surface area, nonyl phenol antibody in load, when being detected, due to Copper-cladding Aluminum Bar titanium dioxide Titanium can be with catalyzing hydrogen peroxide in-situ preparation O2, electrochemical signals are generated, recycle antibody in conjunction with the specific quantification of antigen Influence to electron transport ability is finally realized and is examined using unmarked electrochemical method so that current strength accordingly reduces Survey the building of the biosensor of nonyl phenol.
The technical solution adopted by the invention is as follows:
1. a kind of preparation side of the electrochemistry nonyl phenol sensor based on titania-doped/molybdenum disulfide composite material Method, it is characterised in that the electrochemistry nonyl phenol sensor is by working electrode, titania-doped/molybdenum disulfide composite wood Material, nonyl phenol antibody, bovine serum albumin(BSA) composition；Titania-doped/molybdenum disulfide the composite material is Copper-cladding Aluminum Bar two The two-dimensional nano composite material Cu-TiO of TiOx nano square In-situ reaction molybdenum disulfide2/MoS2；
It is characterized in that, the preparation method includes following preparation step:
A. Cu-TiO is prepared2/MoS2；
B. electrochemistry nonyl phenol sensor is prepared；
Wherein, step a prepares Cu-TiO2/MoS2Specific steps are as follows:
(1) 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita is taken to be added to 3 ~ 10 mL n-BuLis jointly molten In liquid, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water-bath is then carried out at 30 ~ 60 DEG C Ultrasonic treatment, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain two sulphur of copper intercalation Change molybdenum nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 10 ~ 500 mg steps (2) is taken to be added to 5 mL metatitanic acids four In butyl ester, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, is then reacting at 160 ~ 180 DEG C It is reacted 18 ~ 20 hours in kettle；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is selected from one of following: copper sulphate, copper chloride, copper nitrate, organocopper compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The specific steps of step b preparation electrochemistry nonyl phenol sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room It is dried under temperature；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating The nonyl phenol antibody-solutions of 10 μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100 The bovine serum albumin solution of μ g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification Learn nonyl phenol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
2. the application of electrochemica biological sensor prepared by preparation method of the present invention, which is characterized in that including Following applying step:
A. standard solution is prepared: preparing the nonyl phenol standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: being by electrochemica biological sensor prepared by preparation method as described in claim 1 The nonyl phenol standard solution of the various concentration prepared in step a is distinguished drop coating to working electrode surface by working electrode, and 4 DEG C It is saved in refrigerator；
C. working curve is drawn: saturated calomel electrode electrode is used as to reference electrode, platinum electrode as to electrode, with The working electrode that step b has been modified forms three-electrode system, connects electrochemical workstation, and 15 are successively added in a cell The H of 5 mol/L of mL PBS and 20 μ L2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank The response current of standard specimen is denoted asI 0, the response current of the nonyl phenol standard solution containing various concentration is denoted asI i, response current reduction Difference be ΔI = I 0-I i, ΔIWith the mass concentration of nonyl phenol standard solutionCBetween it is linear, draw ΔI?CWork Make curve；
D. the detection of nonyl phenol: the nonyl phenol standard solution in step a is replaced with sample to be tested, according in step b and c Method detected, according to response electrical signal intensity reduce difference DELTAIAnd working curve, obtain nonyl phenol in sample to be tested Content.
Beneficial achievement of the invention
(1) electrochemistry nonyl phenol sensor preparation of the present invention is simple, easy to operate, realizes to the fast of sample Fast, sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) present invention is prepared for New Two Dimensional nano-electrode material Cu-TiO using the method for In-situ reaction for the first time2/MoS2, This method is mainly there are three advantage: first is that, sufficiently and titanium dioxide due to growth in situ of the copper on nano titania square The contact of titanium nano square is acted on using the metal surface plasma body of copper, effectively increases semiconductor substrate electron transmission ability And catalytic activity, although solving, titanium dioxide nanoplate specific surface area is bigger and mesoporous characteristic is suitable for electrochemical-based material Material, but the technical problem that electro-chemical activity is not high and current signal is unstable；Second is that due to molybdenum disulfide sheet two-dimensional nano The load characteristic and nano titania square of material on it fully dispersed, greatly increase electron transmission ability, solve Determined titanium dioxide nanoplate poorly conductive and current responsing signal it is weak and be unfavorable for the technical issues of preparing electrochemical sensor； Third is that since copper ion is in this process not only as intercalation material but also as reaction dopant material, finally using In-situ reaction Method realizes one pot of preparation of the composite material, not only saves time, material loss, and make the Copper-cladding Aluminum Bar of preparation Nano titania square can preferably be evenly spread to above molybdenum disulfide sheet two-dimension nano materials.Therefore, the material Effective preparation, have important scientific meaning and application value；
(3) present invention is for the first time by Cu-TiO2/MoS2Applied in the preparation of electrochemica biological sensor, electricity is significantly improved The strength and stability for flowing signal, substantially increases the detection sensitivity of electrochemical sensor, so that electrochemica biological sensor Realize application in actual operation；The application of the material is also associated biomolecule sensor, such as optical electro-chemistry sensor, electricity It causes chemiluminescence sensor etc. to provide Technical Reference, there is extensive potential use value.
Specific embodiment
1 Cu-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 0.2 mmol mantoquita is taken to be added in 3mL n-butyllithium solution jointly, in nitrogen At gas shielded and 60 DEG C, stir 12 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 60 DEG C Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of copper intercalation Nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 500 mg steps (2) is taken to be added to 5 mL butyl titanates In, after stirring 1 hour, it is slowly added to 0.5 mL hydrofluoric acid while stirring, then reacts in a kettle 18 hours at 160 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is copper sulphate；
The nonpolar solvent is hexane；
The water bath sonicator processing, processing time are 1 hour.
2 Cu-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 1.0 mmol mantoquitas is taken to be added in 5 mL n-butyllithium solutions jointly, in nitrogen At gas shielded and 30 DEG C, stir 24 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 30 DEG C Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of copper intercalation Nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 200 mg steps (2) is taken to be added to 5 mL butyl titanates In, after stirring 1 hour, it is slowly added to 0.6 mL hydrofluoric acid while stirring, then reacts in a kettle 20 hours at 180 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is copper chloride；
The nonpolar solvent is carbon tetrachloride；
The water bath sonicator processing, processing time are 1 hour.
The preparation method of 3 electrochemistry nonyl phenol sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 8 μ L of electrode surface drop coating2/MoS2Colloidal sol, at room temperature It dries；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 μ L of electrode surface drop coating, 10 μ The nonyl phenol antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 μ L concentration of electrode surface drop coating to be 100 μ The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification Learn nonyl phenol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The preparation method of 4 electrochemistry nonyl phenol sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 10 μ L of electrode surface drop coating2/MoS2Colloidal sol, room temperature Under dry；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 10 μ L 10 of electrode surface drop coating The nonyl phenol antibody-solutions of μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 10 μ L concentration of electrode surface drop coating to be 100 μ The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification Learn nonyl phenol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The preparation method of 5 electrochemistry nonyl phenol sensor of embodiment
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room temperature Under dry；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 12 μ L 10 of electrode surface drop coating The nonyl phenol antibody-solutions of μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 12 μ L concentration of electrode surface drop coating to be 100 μ The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrification Learn nonyl phenol sensor；
The Cu-TiO2/g-C3N4Colloidal sol is by the Cu-TiO of 50 mg2/g-C3N4Powder is dissolved in 10 mL ultrapure waters In, and the hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The electrochemistry nonyl phenol sensor of 6 embodiment 1 ~ 5 of embodiment preparation, applied to the detection of nonyl phenol, step is such as Under:
(1) standard solution is prepared: preparing the nonyl phenol standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: by electrochemistry nonyl phenol sensor prepared by preparation method as described in claim 1 For working electrode, the nonyl phenol standard solution for the various concentration prepared in step (1) is distinguished into drop coating to working electrode surface, 4 It is saved in DEG C refrigerator；
(3) working curve is drawn: saturated calomel electrode electrode is used as to reference electrode, platinum electrode as to electrode, with The working electrode that step b has been modified forms three-electrode system, connects electrochemical workstation, and 15 are successively added in a cell The H of 5 mol/L of mL PBS and 20 μ L2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank The response current of standard specimen is denoted asI 0, the response current of the nonyl phenol standard solution containing various concentration is denoted asI i, response current reduction Difference be ΔI = I 0-I i, ΔIWith the mass concentration of nonyl phenol standard solutionCBetween it is linear, draw ΔI?CWork Make curve；The linear detection range of nonyl phenol are as follows: 0.009 ~ 200 ng/mL, detection limit are as follows: 3.0 pg/mL；
(4) detection of nonyl phenol: replacing the nonyl phenol standard solution in step (1) with sample to be tested, according to step (2) and (3) method in is detected, the difference DELTA that electrical signal intensity reduces according to responseIAnd working curve, it obtains in sample to be tested The content of nonyl phenol.

Claims (1)

1. a kind of preparation method of the electrochemistry nonyl phenol sensor based on titania-doped/molybdenum disulfide composite material, Electrochemistry nonyl phenol sensor described in being characterized in that is by working electrode, titania-doped/molybdenum disulfide composite material, nonyl Phenol antibody, bovine serum albumin(BSA) composition；Titania-doped/molybdenum disulfide the composite material is received for copper-doped titanium dioxide The two-dimensional nano composite material Cu-TiO of rice square In-situ reaction molybdenum disulfide2/MoS2；
The Cu-TiO2/MoS2Specific preparation step are as follows: take 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita It is added in 3 ~ 10 mL n-butyllithium solutions jointly, at nitrogen protection and 30 ~ 60 DEG C, stirs 12 ~ 48 hours, obtain Solution after reaction；Using the solution after nonpolar solvent washing reaction, then carried out at water bath sonicator at 30 ~ 60 DEG C Reason, after handle, solution after recycling nonpolar solvent carrying out washing treatment is dried in vacuo, the molybdenum disulfide for obtaining copper intercalation receives Rice material；It takes the molybdenum disulfide nano material of copper intercalation made from 10 ~ 500 mg to be added in 5 mL butyl titanates, stirs After 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, then react 18 at 160 ~ 180 DEG C in a kettle ~ 20 hours；Resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, be dried in vacuo, obtain at 50 DEG C Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is selected from one of following: copper sulphate, copper chloride, copper nitrate, organocopper compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The specific preparation step of the electrochemistry nonyl phenol sensor are as follows:
(1) using glass-carbon electrode as working electrode, in the Cu-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol dries in the air at room temperature It is dry；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating, 10 μ The nonyl phenol antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100 μ g/ The bovine serum albumin solution of mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains electrochemistry nonyl Base phenol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and ultrasound The hydrosol obtained after 30 min；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
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CN105572193A (en) * 2016-02-25 2016-05-11 王亚莉 Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite
CN105699368B (en) * 2016-03-16 2018-07-06 济南大学 A kind of preparation method and application of the difunctional hydrogen peroxide without enzyme sensor based on Two-dimensional Composites structure
CN105675689B (en) * 2016-03-16 2018-06-01 济南大学 A kind of preparation method and application of the hydrogen peroxide without enzyme sensor based on vulcanization molybdenum composite material structure

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