CN106248753A - A kind of preparation method of Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer - Google Patents

A kind of preparation method of Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer Download PDF

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CN106248753A
CN106248753A CN201610521714.6A CN201610521714A CN106248753A CN 106248753 A CN106248753 A CN 106248753A CN 201610521714 A CN201610521714 A CN 201610521714A CN 106248753 A CN106248753 A CN 106248753A
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spanon
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CN106248753B (en
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张勇
吴丹
李贺
任祥
魏琴
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University of Jinan
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Abstract

The invention discloses the preparation method of a kind of Optical Electro-Chemistry Spanon sensor.Belong to Nano-function thin films and biosensor technology field.A kind of novel supported bimetallic codope photosensitizer, i.e. the two-dimensional nano composite FeCo TiO of ferrum, cobalt codoping titanium dioxide nano 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, Spanon 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 Spanon.

Description

A kind of Optical Electro-Chemistry Spanon based on load type double-metal codope photosensitizer senses The preparation method of device
Technical field
The present invention relates to the preparation method of a kind of Optical Electro-Chemistry Spanon sensor.Belong to Nano-function thin films and life Thing sensor technical field.
Background technology
Spanon is a kind of agricultural chemical insecticide, and in soil, Spanon can be slightly deep to soil by the eluviation of water Layer migrates.The animal of Spanon chronic poisoning may occur in which under weight loss, packed cell volume, hemoglobin and red blood cell count(RBC) Fall, leukocyte count increase etc., according to the WHO of 1972, if human body Long Term Contact Spanon can cause canceration.
At present, the method for detection Spanon 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 Spanon 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 Spanon sensor, prepared sensor, can be used for quick, the Sensitive Detection of Spanon.Based on this purpose, A kind of novel supported bimetallic codope photosensitizer, i.e. ferrum, cobalt codoping titanium dioxide nano side are the method comprises the steps of firstly, preparing Block and the two-dimensional nano composite FeCo-TiO of molybdenum bisuphide In-situ reaction2/MoS2, utilize the good biofacies of this material Capacitive and big specific surface area, Spanon antibody, fixing upper alkali phosphatase in load, when detecting, due to alkalescence phosphorus Acid enzyme can be catalyzed L-AA-2-tricresyl phosphate sodium salt AAP and produce L-AA AA in situ, and and then carries for Photoelectric Detection Supplied for electronic donor, recycling antibody is combined the impact on electron transport ability with the specific quantification of antigen so that photoelectric current is strong Degree is corresponding to be reduced, and finally achieves the structure of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection Spanon.
The technical solution used in the present invention is as follows:
1. a preparation method for Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer, it is special Levy and be that described load type double-metal codope photosensitizer is that ferrum, cobalt codoping titanium dioxide nano square are former with molybdenum bisuphide The two-dimensional nano composite FeCo-TiO that position is compound2/MoS2, described Optical Electro-Chemistry Spanon sensor by working electrode, FeCo-TiO2/MoS2, Spanon antibody, alkali phosphatase, bovine serum albumin composition；
It is characterized in that, described preparation method includes following preparation process:
A. FeCo-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry Spanon sensor is prepared；
Wherein, step a prepares FeCo-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 cobalt 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, cobalt intercalation altogether Change molybdenum nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 ~ 500 mg steps (2), cobalt 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 FeCo-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 cobalt salt is selected from one of following: cobaltous sulfate, cobaltous chloride, cobalt nitrate, cobalt acetate, organic cobalt compounds；
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 Spanon sensor:
(1) with ITO electro-conductive glass as working electrode, at the FeCo-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 Spanon 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 Spanon sensor；
Described FeCo-TiO2/MoS2Colloidal sol is by the FeCo-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 Spanon sensor prepared by preparation method the most of the present invention, it is characterised in that Including following applying step:
A. standard solution preparation: prepare the Spanon standard solution of one group of variable concentrations including blank standard specimen；
B. working electrode is modified: by the Optical Electro-Chemistry Spanon sensor prepared by preparation method as claimed in claim 1 be Working electrode, by the drop coating respectively of the Spanon 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 Spanon concentration of standard solution of gained, drawing Curve；
D. the detection of Spanon: replace the Spanon standard solution in step a with testing sample, according to the side in step b and c Method detects, and according to intensity level and the working curve of response signal, obtains the content of Spanon in testing sample.
The useful achievement of the present invention
(1) Optical Electro-Chemistry Spanon sensor of the present invention preparation is simple, easy to operate, it is achieved that to sample quick, Selective enumeration method 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 FeCo-TiO first2/MoS2, the method master There are three advantages: one is, and titanium dioxide abundant due to ferrum, the cobalt growth in situ on nano titania square jointly Nano square contacts, and utilizes ferrum, the metal surface plasma body effect of cobalt 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, cobalt 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 cobalt doped 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 FeCo-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 FeCo-TiO2/MoS2Preparation
(1) taking 0.6 g molybdenum disulfide powder, 0.2 mmol iron salt and 0.2 mmol cobalt 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, cobalt intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 500 mg steps (2), cobalt 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 FeCo-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 cobalt salt is cobaltous sulfate；
Described non-polar solven is hexane；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 2 FeCo-TiO2/MoS2Preparation
(1) taking 0.6 g molybdenum disulfide powder, 1.0 mmol iron salt and 1.0 mmol cobalt salts, 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, cobalt intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 200 mg steps (2), cobalt 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 FeCo-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 cobalt salt is cobaltous chloride；
Described non-polar solven is carbon tetrachloride；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 3 FeCo-TiO2/MoS2Preparation
(1) take 0.6 g molybdenum disulfide powder, 2.0 mmol iron salt and 2.0 mmol cobalt salts 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, cobalt intercalation altogether Nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 mg steps (2), cobalt 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 FeCo-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 cobalt salt is cobalt 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 Spanon sensor
(1) using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, at the FeCo-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 Spanon 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 Spanon sensor；
Described FeCo-TiO2/MoS2Colloidal sol is by the FeCo-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 Spanon sensor
All preparation processes are with embodiment 4, the FeCo-TiO of a middle use2/MoS2Prepared by embodiment 2 FeCo-TiO2/MoS2。
The preparation method of embodiment 6 Optical Electro-Chemistry Spanon sensor
All preparation processes are with embodiment 4, the FeCo-TiO of a middle use2/MoS2Prepared by embodiment 3 FeCo-TiO2/MoS2。
The Optical Electro-Chemistry Spanon sensor of embodiment 7 embodiment 1 and 3 preparation, is applied to the detection of Spanon, step As follows:
(1) standard solution preparation: prepare the Spanon standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry Spanon sensor prepared by preparation method as claimed in claim 1 be Working electrode, by the drop coating respectively of the Spanon 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 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 Spanon concentration of standard solution of gained, drawing Curve；The linear detection range of Spanon is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the Spanon standard solution in step (1) with testing sample, according to step (2) and (3) In method detect, according to the response intensity level of signal and working curve, obtain the content of Spanon in testing sample.
The Optical Electro-Chemistry Spanon sensor of embodiment 8 embodiment 2 and 4 preparation, is applied to the detection of Spanon, step As follows:
(1) standard solution preparation: prepare the Spanon standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry Spanon sensor prepared by preparation method as claimed in claim 1 be Working electrode, by the drop coating respectively of the Spanon 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 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 Spanon concentration of standard solution of gained, drawing Curve；The linear detection range of Spanon is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the Spanon standard solution in step (1) with testing sample, according to step (2) and (3) In method detect, according to the response intensity level of signal and working curve, obtain the content of Spanon in testing sample.
The Optical Electro-Chemistry Spanon sensor of embodiment 9 embodiment 3 and 6 preparation, is applied to the detection of Spanon, step As follows:
(1) standard solution preparation: prepare the Spanon standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: by the Optical Electro-Chemistry Spanon sensor prepared by preparation method as claimed in claim 1 be Working electrode, by the drop coating respectively of the Spanon 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 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 Spanon concentration of standard solution of gained, drawing Curve；The linear detection range of Spanon is: 0.002 ~ 200 ng/mL, and detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the Spanon standard solution in step (1) with testing sample, according to step (2) and (3) In method detect, according to the response intensity level of signal and working curve, obtain the content of Spanon in testing sample.

Claims (4)

1. a preparation method for Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer, its feature It is that described load type double-metal codope photosensitizer is ferrum, cobalt codoping titanium dioxide nano square and molybdenum bisuphide original position Compound two-dimensional nano composite FeCo-TiO2/MoS2, described Optical Electro-Chemistry Spanon sensor by working electrode, FeCo-TiO2/MoS2, Spanon antibody, alkali phosphatase, bovine serum albumin composition.
2. the system of Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer as claimed in claim 1 Preparation Method, it is characterised in that described preparation method includes following two preparation process:
A. FeCo-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry Spanon sensor is prepared.
3. the Optical Electro-Chemistry Spanon sensor based on load type double-metal codope photosensitizer as described in claim 1 and 2 Preparation method, it is characterised in that described FeCo-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 cobalt 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, cobalt intercalation altogether Change molybdenum nano material；
(3) the molybdenum disulfide nano material taking the prepared ferrum of 10 ~ 500 mg steps (2), cobalt 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 FeCo-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 cobalt salt is selected from one of following: cobaltous sulfate, cobaltous chloride, cobalt nitrate, cobalt acetate, organic cobalt compounds；
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 Spanon sensor based on load type double-metal codope photosensitizer as described in claim 1 and 2 Preparation method, it is characterised in that the concrete preparation process of described Optical Electro-Chemistry Spanon sensor is:
(1) with ITO electro-conductive glass as working electrode, at the FeCo-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 Spanon 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 Spanon sensor；
Described FeCo-TiO2/MoS2Colloidal sol is by the FeCo-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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112379098A (en) * 2020-11-05 2021-02-19 集美大学 ELISA detection method for mimic enzyme-labeled antibody of histamine content in aquatic product

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060239907A1 (en) * 2003-06-03 2006-10-26 The Trustees Of The University Of Pennsylvania Stealthy nano agents
CN103913565A (en) * 2014-04-26 2014-07-09 济南大学 Preparation method and application of immunosensor constructed by difunctional marker
CN105572197A (en) * 2016-02-25 2016-05-11 济南大学 Preparation method and application of photoelectrochemical estradiol sensor based on magnetic photosensitive nanomaterial
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
CN105628758A (en) * 2016-02-25 2016-06-01 济南大学 Preparation method and application for photoelectrochemical parathion sensor based on two-dimensional nanometer light-sensitive material
CN105675689A (en) * 2016-03-16 2016-06-15 济南大学 Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060239907A1 (en) * 2003-06-03 2006-10-26 The Trustees Of The University Of Pennsylvania Stealthy nano agents
CN103913565A (en) * 2014-04-26 2014-07-09 济南大学 Preparation method and application of immunosensor constructed by difunctional marker
CN105572197A (en) * 2016-02-25 2016-05-11 济南大学 Preparation method and application of photoelectrochemical estradiol sensor based on magnetic photosensitive nanomaterial
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
CN105628758A (en) * 2016-02-25 2016-06-01 济南大学 Preparation method and application for photoelectrochemical parathion sensor based on two-dimensional nanometer light-sensitive material
CN105675689A (en) * 2016-03-16 2016-06-15 济南大学 Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KE-JING HUANG等: "Amperometric immunobiosensor for α-fetoprotein using Au nanoparticles/chitosan/TiO2–graphene composite based platform", 《BIOELECTROCHEMISTRY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112379098A (en) * 2020-11-05 2021-02-19 集美大学 ELISA detection method for mimic enzyme-labeled antibody of histamine content in aquatic product

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