CN106198682A - A kind of preparation method of Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent - Google Patents

A kind of preparation method of Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent Download PDF

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CN106198682A
CN106198682A CN201610521792.6A CN201610521792A CN106198682A CN 106198682 A CN106198682 A CN 106198682A CN 201610521792 A CN201610521792 A CN 201610521792A CN 106198682 A CN106198682 A CN 106198682A
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furazolidone
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张勇
马洪敏
杜斌
胡丽华
庞雪辉
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Abstract

The invention discloses the preparation method of a kind of Optical Electro-Chemistry furazolidone sensor.Belong to Nano-function thin films and biosensor technology field.A kind of novel dual metal codope two-dimensional light sensitive agent, i.e. the two-dimensional nano composite FeMn TiO of ferrum, manganese codoped nano titania square and molybdenum bisuphide In-situ reaction are the method comprises the steps of firstly, preparing2/MoS2Utilize the good biocompatibility of this material and big specific surface area, furazolidone antibody, fixing upper alkali phosphatase in load, when detecting, L ascorbic acid AA is produced in situ owing to alkali phosphatase can be catalyzed L ascorbic acid 2 tricresyl phosphate sodium salt AAP, and and then for Photoelectric Detection provide electron donor, recycling antibody is combined the impact on electron transport ability with the specific quantification of antigen, photo-current intensity is reduced accordingly, finally achieves the structure of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection furazolidone.

Description

A kind of Optical Electro-Chemistry furazolidone based on bimetallic codope two-dimensional light sensitive agent senses The preparation method of device
Technical field
The present invention relates to the preparation method of a kind of Optical Electro-Chemistry furazolidone sensor.Belong to Nano-function thin films with Biosensor technology field.
Background technology
Furazolidone (furazolidone) is a kind of Nitrofuran antibiotics, for broad spectrum antibiotic.When using as veterinary drug, furan Oxazolone of muttering has good drug effect to preventing and treating some protozoacide, fish molds, bacterial gill rot disease, erythroderma, hemorrhagic disease etc..In aquaculture In, furazolidone can be used for treating animal and bird intestines to be infected, as yellow in piglet, Hakuri.In aquatic products industry, furazolidone is to Salmonoidei sense Dye Myxosoma cerebralis has certain curative effect.But furazolidone is classified as the medicine prohibitted the use of by the Ministry of Agriculture of China, must not eat in animality Product detect.FDA also prohibited the itrofurans (including furazolidone) use in animal food in 2002.
At present, the method for detection furazolidone mainly has chromatography, mass spectrography etc..This type of method instrument is valuable, operation is multiple Miscellaneous, laboratory personnel just can detect after needing professional training.Therefore, R&D costs are low, detect fast, highly sensitive, specificity Strong furazolidone sensor is significant.
Optical Electro-Chemistry sensor is due to the feature such as highly sensitive, testing cost is low, in recent years by increasing researcher Paid close attention to.Optical Electro-Chemistry sensor is to cause electron-hole pair to separate based on additional light source activation Electrophotosensitivmaterial material, The most partially under potential condition, it is achieved the electronics quick transmission on electrode, quasiconductor and trim and analyte, and form light Electric current.In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, and recycling biological immune combines, Just can realize the qualitative and quantitative analysis to analyte according to the change of photoelectric current.
Optical Electro-Chemistry sensor most critical technology is exactly the raising of the performances such as the size to photoelectric current and stability.Titanium dioxide Titanium is a kind of photocatalyst and light induced electron host material being most widely used, but, the reality of titanium dioxide to be given full play to Border application level, needs one side to improve Optical Electro-Chemistry work by regulating and controlling its material morphology to expose more high activity crystal faces Property, on the other hand improve the sun by doping different metal or metal-oxide regulation and control photosensitive wavelength to visible-range extension The utilization rate of light.Due to two dimension titanium dioxide nano material, such as titanium dioxide nanoplate, nano titania square etc., it is possible to Exposing more high activity crystal face, have higher Optical Electro-Chemistry activity, titanium dioxide nanoplate has more preferable than nanoparticle Ground application prospect, the research for titanium dioxide nanoplate also receives much concern.And single titanium dioxide nano material is photosensitive Wavelength is typically in ultra-violet (UV) band, and interacts due to bad dispersibility, easily stacking, thus reduces Optical Electro-Chemistry activity, unfavorable Apply in reality.Therefore, R&D costs are low, photosensitive dose active of titanium dioxide has important to prepare simple high Optical Electro-Chemistry Scientific meaning and using value.
(chemical formula is MoS to molybdenum bisuphide2) nano material, there is two-dimensional layered structure, be most widely used solid profit One of lubrication prescription.Lamellar two-dimension nano materials after its stripping, is the semiconductor nano material of excellent performance, except having big ratio Surface area, can improve load capacity as catalyst and the carrier of biological antibody, also has simultaneously as promoter excellent Electron transmission performance.
At present, most synthesizing mean be all be separately synthesized after, then catalyst is combined with carrier, process is numerous Trivial, productivity is the highest.Therefore, have before the photosensitizer of excellent photoelectrochemical behaviour has a wide range of applications for In-situ reaction preparation Scape and important scientific meaning.
Additionally, the photo-generate electron-hole of single titanium dioxide nano material is to the most compound, thus cause photosignal Weaken, and titanium dioxide poorly conductive also limit the Optical Electro-Chemistry sensor that built by single titanium dioxide nano material Sensitivity is the highest, is unfavorable for actual application.Therefore, design, prepare efficient, stable doping titanium dioxide nano sheet and Trim is the key technology preparing Optical Electro-Chemistry sensor.
Summary of the invention
It is an object of the invention to provide a kind of prepare simple, highly sensitive, detection quickly, the Optical Electro-Chemistry of high specificity The preparation method of furazolidone sensor, prepared sensor, can be used for quick, the Sensitive Detection of furazolidone.Based on this Purpose, the method comprises the steps of firstly, preparing a kind of novel dual metal codope two-dimensional light sensitive agent, i.e. ferrum, manganese codoped nano titania Square and the two-dimensional nano composite FeMn-TiO of molybdenum bisuphide In-situ reaction2/MoS2, utilize the good biology of this material The compatibility and big specific surface area, furazolidone antibody, fixing upper alkali phosphatase in load, when detecting, due to alkali Acid phosphatase can be catalyzed L-AA-2-tricresyl phosphate sodium salt AAP and produce L-AA AA in situ, and and then is light electric-examination Surveying and provide electron donor, recycling antibody is combined the impact on electron transport ability with the specific quantification of antigen so that photoelectricity Intensity of flow reduces accordingly, finally achieves the structure of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection furazolidone Build.
The technical solution used in the present invention is as follows:
1. a preparation method for Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent, it is special Levy and be that described bimetallic codope two-dimensional light sensitive agent is ferrum, manganese codoped nano titania square and molybdenum bisuphide original position Compound two-dimensional nano composite FeMn-TiO2/MoS2, described Optical Electro-Chemistry furazolidone sensor by working electrode, FeMn-TiO2/MoS2, furazolidone antibody, alkali phosphatase, bovine serum albumin composition；
It is characterized in that, described preparation method includes following preparation process:
A. FeMn-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry furazolidone sensor is prepared；
Wherein, step a prepares FeMn-TiO2/MoS2Concretely comprise the following steps:
(1) take 0.6 g molybdenum disulfide powder, 0.2 ~ 2.0 mmol iron salt and 0.2 ~ 2.0 mmol manganese salt jointly join 3 ~ In 10 mL n-butyllithium solutions, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, obtain reacted molten Liquid；
(2) utilize reacted solution in non-polar solven washing step (1), at 30 ~ 60 DEG C, then carry out water bath sonicator Process, after having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain two sulfur of ferrum, manganese intercalation altogether Change molybdenum nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 ~ 500 mg steps (2), manganese intercalation altogether joins 5 mL metatitanic acids In four butyl esters, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL Fluohydric acid. while stirring, then instead at 160 ~ 200 DEG C Answer in still and react 18 ~ 24 hours；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, at 50 DEG C, vacuum is done Dry, i.e. prepare FeMn-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described iron salt is selected from one of following: iron sulfate, iron chloride, ferric nitrate, ferric acetate, organoiron compound；
Described manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, organo-manganese compound；
Described non-polar solven is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
Described water bath sonicator processes, and the process time is 1 hour；
Step b prepares concretely comprising the following steps of Optical Electro-Chemistry furazolidone sensor:
(1) with ITO electro-conductive glass as working electrode, at the FeMn-TiO of electrode surface drop coating 8 ~ 12 L2/MoS2Colloidal 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 furazolidone 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 6 ~ 10 L concentration is 20 g/ The alkaline phosphatase enzymatic solution of mL, preserves in 4 DEG C of refrigerators and dries；
(4) the electrode PBS that will obtain in step (3), 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；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry Furazolidone sensor；
Described FeMn-TiO2/MoS2Colloidal sol is by the FeMn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultra-pure waters, 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.
The application of the Optical Electro-Chemistry furazolidone sensor prepared by preparation method the most of the present invention, its feature exists In, including following applying step:
A. standard solution preparation: prepare the furazolidone standard solution of one group of variable concentrations including blank standard specimen；
B. working electrode is modified: by the Optical Electro-Chemistry furazolidone sensor prepared by preparation method as claimed in claim 1 For working electrode, by the drop coating respectively of the furazolidone standard solution of the variable concentrations of preparation in step b to working electrode surface, 4 DEG C refrigerator preserves；
C. working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step b institute The working electrode composition three-electrode system modified, is connected on Optical Electro-Chemistry detection equipment；Successively add in a cell The Tris HCl buffer solution of 15mL pH=9.6 and the L-AA-2-tricresyl phosphate sodium salt AAP of 5 mL 10 mmol/L are molten Liquid；Use i-t means of testing, according to the relation between photocurrent values and the furazolidone concentration of standard solution of gained, draw work Make curve；
D. the detection of furazolidone: replace the furazolidone standard solution in step a with testing sample, according in step b and c Method detect, according to the response intensity level of signal and working curve, obtain the content of furazolidone in testing sample.
The useful achievement of the present invention
(1) Optical Electro-Chemistry furazolidone sensor of the present invention preparation is simple, easy to operate, it is achieved that fast to sample Selective enumeration method fast, sensitive, high, and low cost, can be applicable to portable inspectiont, has market development prospect；
(2) present invention uses the method for In-situ reaction to be prepared for novel photocatalyst FeMn-TiO first2/MoS2, the method master There are three advantages: one is, and titanium dioxide abundant due to ferrum, the manganese growth in situ on nano titania square jointly Nano square contacts, and utilizes ferrum, the metal surface plasma body effect of manganese and the synergism of the two, effectively prevents photoproduction Being combined of electron-hole pair, drastically increases photocatalytic activity, due to the effect of metal ion, has widened photosensitive wavelength ground Scope, it is achieved that in visible region ground photocatalysis, drastically increases sunlight ground utilization ratio, solves two dimension dioxy Although it is good to change titanium nano material photocatalysis effect, but the technical problem of photocatalysis effect difference under sunlight；Two are, by In the load characteristic of molybdenum bisuphide lamellar two-dimension nano materials and nano titania square thereon fully dispersed, greatly With solving two dimension titanium dioxide nano material, the photocatalytic activity increasing nano titania square is unfavorable for that dispersion is dropped The technical problem of low photocatalytic activity；Three are, due to iron ion, manganese ion the most not only as intercalation material but also as anti- Answer dopant material, finally use the method for In-situ reaction to achieve one pot of preparation of this composite, not only save time, material Material loss, and make the ferrum of preparation, the nano titania square of additive Mn can preferably evenly spread to molybdenum bisuphide Above lamellar two-dimension nano materials.Therefore, effective preparation of this material, there is important scientific meaning and using value；
(3) present invention is first by FeMn-TiO2/MoS2It is applied in the preparation of Photoelectrochemistrbiosensor biosensor, significantly improves The valid density of photo-generated carrier, substantially increases the detection sensitivity of Optical Electro-Chemistry sensor so that Optical Electro-Chemistry biology passes Sensor achieves the application in real work；The application of this material, is also associated biomolecule sensor, as electrogenerated chemiluminescence passes Sensor, electrochemical sensor etc. provide Technical Reference, have the most potential use value.
Detailed description of the invention
Embodiment 1 FeMn-TiO2/MoS2Preparation
(1) taking 0.6 g molybdenum disulfide powder, 0.2 mmol iron salt and 0.2 mmol manganese salt, jointly to join 3mL n-BuLi molten In liquid, at nitrogen protection and 60 DEG C, stir 12 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 60 DEG C, then carry out water bath sonicator process, After having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum bisuphide of ferrum, manganese intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 500 mg steps (2), manganese intercalation altogether joins 5 mL butyl titanates In, after stirring 1 hour, it is slowly added to 0.5 mL Fluohydric acid. while stirring, then reacts 18 hours in a kettle. at 160 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, at 50 DEG C, vacuum is done Dry, i.e. prepare FeMn-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described iron salt is iron sulfate；
Described manganese salt is manganese sulfate；
Described non-polar solven is hexane；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 2 FeMn-TiO2/MoS2Preparation
(1) taking 0.6 g molybdenum disulfide powder, 1.0 mmol iron salt and 1.0 mmol manganese salt, jointly to join 5 mL n-BuLis molten In liquid, at nitrogen protection and 30 DEG C, stir 24 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 30 DEG C, then carry out water bath sonicator process, After having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum bisuphide of ferrum, manganese intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 200 mg steps (2), manganese intercalation altogether joins 5 mL butyl titanates In, after stirring 1 hour, it is slowly added to 0.6 mL Fluohydric acid. while stirring, then reacts 20 hours in a kettle. at 180 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, at 50 DEG C, vacuum is done Dry, i.e. prepare FeMn-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described iron salt is iron chloride；
Described manganese salt is manganese chloride；
Described non-polar solven is carbon tetrachloride；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 3 FeMn-TiO2/MoS2Preparation
(1) take 0.6 g molybdenum disulfide powder, 2.0 mmol iron salt and 2.0 mmol manganese salt and jointly join 10 mL n-BuLis In solution, at nitrogen protection and 50 DEG C, stir 48 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 50 DEG C, then carry out water bath sonicator process, After having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum bisuphide of ferrum, manganese intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 mg steps (2), manganese intercalation altogether joins 5 mL butyl titanates In, after stirring 1 hour, it is slowly added to 0.8 mL Fluohydric acid. while stirring, then reacts 24 hours in a kettle. at 200 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, at 50 DEG C, vacuum is done Dry, i.e. prepare FeMn-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described iron salt is ferric acetate；
Described manganese salt is manganese acetate；
Described non-polar solven is benzene；
Described water bath sonicator processes, and the process time is 1 hour.
The preparation method of embodiment 4 Optical Electro-Chemistry furazolidone sensor
(1) using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, at the FeMn-of electrode surface drop coating 8 L TiO2/MoS2Colloidal 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 Furazolidone 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), continuing in electrode surface drop coating 6 L concentration is 20 g/mL's Alkaline phosphatase enzymatic solution, preserves in 4 DEG C of refrigerators and dries；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry Furazolidone sensor；
Described FeMn-TiO2/MoS2Colloidal sol is by the FeMn-TiO prepared by the embodiment 1 of 50 mg2/MoS2Powder is dissolved in In 10 mL ultra-pure waters, 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.
The preparation method of embodiment 5 Optical Electro-Chemistry furazolidone sensor
All preparation processes are with embodiment 4, the FeMn-TiO of a middle use2/MoS2Prepared by embodiment 2 FeMn-TiO2/MoS2。
The preparation method of embodiment 6 Optical Electro-Chemistry furazolidone sensor
All preparation processes are with embodiment 4, the FeMn-TiO of a middle use2/MoS2Prepared by embodiment 3 FeMn-TiO2/MoS2。
The Optical Electro-Chemistry furazolidone sensor of embodiment 7 embodiment 1 and 3 preparation, is applied to the detection of furazolidone, Step is as follows:
(1) standard solution preparation: prepare the furazolidone standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry furazolidone sensor prepared by preparation method as claimed in claim 1 For working electrode, by the drop coating respectively of the furazolidone standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step (2) The working electrode composition three-electrode system modified, is connected on Optical Electro-Chemistry detection equipment；Successively add in a cell The Tris HCl buffer solution of 15mL pH=9.6 and the L-AA-2-tricresyl phosphate sodium salt AAP of 5 mL 10 mmol/L are molten Liquid；Use i-t means of testing, according to the relation between photocurrent values and the furazolidone concentration of standard solution of gained, draw work Make curve；The linear detection range of furazolidone is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the furazolidone standard solution in step (1) with testing sample, according to step (2) and (3) method in detects, and according to the response intensity level of signal and working curve, obtains containing of furazolidone in testing sample Amount.
The Optical Electro-Chemistry furazolidone sensor of embodiment 8 embodiment 2 and 4 preparation, is applied to the detection of furazolidone, Step is as follows:
(1) standard solution preparation: prepare the furazolidone standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry furazolidone sensor prepared by preparation method as claimed in claim 1 For working electrode, by the drop coating respectively of the furazolidone standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step (2) The working electrode composition three-electrode system modified, is connected on Optical Electro-Chemistry detection equipment；Successively add in a cell The Tris HCl buffer solution of 15mL pH=9.6 and the L-AA-2-tricresyl phosphate sodium salt AAP of 5 mL 10 mmol/L are molten Liquid；Use i-t means of testing, according to the relation between photocurrent values and the furazolidone concentration of standard solution of gained, draw work Make curve；The linear detection range of furazolidone is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the furazolidone standard solution in step (1) with testing sample, according to step (2) and (3) method in detects, and according to the response intensity level of signal and working curve, obtains containing of furazolidone in testing sample Amount.
The Optical Electro-Chemistry furazolidone sensor of embodiment 9 embodiment 3 and 6 preparation, is applied to the detection of furazolidone, Step is as follows:
(1) standard solution preparation: prepare the furazolidone standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry furazolidone sensor prepared by preparation method as claimed in claim 1 For working electrode, by the drop coating respectively of the furazolidone standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step (2) The working electrode composition three-electrode system modified, is connected on Optical Electro-Chemistry detection equipment；Successively add in a cell The Tris HCl buffer solution of 15mL pH=9.6 and the L-AA-2-tricresyl phosphate sodium salt AAP of 5 mL 10 mmol/L are molten Liquid；Use i-t means of testing, according to the relation between photocurrent values and the furazolidone concentration of standard solution of gained, draw work Make curve；The linear detection range of furazolidone is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the furazolidone standard solution in step (1) with testing sample, according to step (2) and (3) method in detects, and according to the response intensity level of signal and working curve, obtains containing of furazolidone in testing sample Amount.

Claims (4)

1. a preparation method for Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent, its feature It is that described bimetallic codope two-dimensional light sensitive agent is that ferrum, manganese codoped nano titania square and molybdenum bisuphide are the most multiple The two-dimensional nano composite FeMn-TiO closed2/MoS2, described Optical Electro-Chemistry furazolidone sensor by working electrode, FeMn-TiO2/MoS2, furazolidone antibody, alkali phosphatase, bovine serum albumin composition.
2. the system of Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent as claimed in claim 1 Preparation Method, it is characterised in that described preparation method includes following two preparation process:
A. FeMn-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry furazolidone sensor is prepared.
3. the Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent as described in claim 1 and 2 Preparation method, it is characterised in that described FeMn-TiO2/MoS2Concrete preparation process be:
(1) take 0.6 g molybdenum disulfide powder, 0.2 ~ 2.0 mmol iron salt and 0.2 ~ 2.0 mmol manganese salt jointly join 3 ~ In 10 mL n-butyllithium solutions, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, obtain reacted molten Liquid；
(2) utilize reacted solution in non-polar solven washing step (1), at 30 ~ 60 DEG C, then carry out water bath sonicator Process, after having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain two sulfur of ferrum, manganese intercalation altogether Change molybdenum nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 ~ 500 mg steps (2), manganese intercalation altogether joins 5 mL metatitanic acids In four butyl esters, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL Fluohydric acid. while stirring, then instead at 160 ~ 200 DEG C Answer in still and react 18 ~ 24 hours；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, at 50 DEG C, vacuum is done Dry, i.e. prepare FeMn-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described iron salt is selected from one of following: iron sulfate, iron chloride, ferric nitrate, ferric acetate, organoiron compound；
Described manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, organo-manganese compound；
Described non-polar solven is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
Described water bath sonicator processes, and the process time is 1 hour.
4. the Optical Electro-Chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent as described in claim 1 and 2 Preparation method, it is characterised in that the concrete preparation process of described Optical Electro-Chemistry furazolidone sensor is:
(1) with ITO electro-conductive glass as working electrode, at the FeMn-TiO of electrode surface drop coating 8 ~ 12 L2/MoS2Colloidal 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 furazolidone 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 6 ~ 10 L concentration is 20 g/ The alkaline phosphatase enzymatic solution of mL, preserves in 4 DEG C of refrigerators and dries；
(4) the electrode PBS that will obtain in step (3), 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；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry Furazolidone sensor；
Described FeMn-TiO2/MoS2Colloidal sol is by the FeMn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultra-pure waters, 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.
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