CN108918618A - A kind of Dopamine Sensor and its preparation and application based on sulfonated graphene supported palladium - Google Patents
A kind of Dopamine Sensor and its preparation and application based on sulfonated graphene supported palladium Download PDFInfo
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- CN108918618A CN108918618A CN201811005400.6A CN201811005400A CN108918618A CN 108918618 A CN108918618 A CN 108918618A CN 201811005400 A CN201811005400 A CN 201811005400A CN 108918618 A CN108918618 A CN 108918618A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention belongs to electrochemical sensor technology field, a kind of Dopamine Sensor based on sulfonated graphene supported palladium and its preparation and application are disclosed.The sensor is formed by reference electrode, to the working electrode after electrode and modification, working electrode after the modification is by working electrode and is solidificated in the material identification film of working electrode surface and forms, wherein, the material identification film mainly loads palladium composite material by sulfonated graphene and perfluorinated sulfonic resin is prepared.Sensor of the invention has good selectivity, reproducibility and stability, and electrode catalyst performance is good, can accurately be detected to dopamine, strong antijamming capability；There is wider detection range, lower detection limit simultaneously.Method of the invention is simple, at low cost.Prepared sensor is for detecting dopamine.
Description
Technical field
The invention belongs to electrochemical sensor technology fields, and in particular to a kind of detection based on sulfonated graphene supported palladium
Dopamine without enzyme sensor and the preparation method and application thereof.
Background technique
Dopamine is that internal norepinephrine or adrenaline are raw as a kind of important Catecholamines Neurotransmitters in Blood
The precursor of object synthesis is present in diplomatic all sympathetic nerve, neuromere and central nervous system, has and adjust renal function, swash
The important function such as element secretion.Many diseases, such as epilepsy, Parkinson's disease, schizophrenia, all have with dopamine concentration extremely
It closes.Dopamine is also related with the mood of people, lust etc., it is to transmit the happily molecule with excitement, and dopamine is normal in human body
Mass concentration is 0.2-0.4 μ g/mL.When DOPAMINE CONTENT IN RABBIT decline, people can feel fatigue often, when DOPAMINE CONTENT IN RABBIT rises
When, human body can feel excited.If DOPAMINE CONTENT IN RABBIT increases always or is in a high level, human body can keep excited shape
State is easily addicting.Thus the research detection of dopamine has the research of neuro-physiology, clinical application, pharmaceutics etc.
Important meaning.
Currently, the detection method of dopamine mainly has：High performance liquid chromatography, fluorescent spectrometry, capillary electrophoresis, purple
Outer spectrophotometry etc..The technical operation that traditional measuring method instrument is complicated, needs a large amount of sample reagent, need to have profession
Personnel, detection time be long, costly, the more disadvantage of interference.And electrochemical detection method have have higher knowledge to object
Other ability, amount of samples is few, response is fast, at low cost, small in size, convenient for universal advantage, therefore, chooses suitable catalysis material
Expect, easy, quick, accurate, high sensitivity the electrochemistry Dopamine Sensor of preparation research and development there will be great answer on clinical medicine
Use prospect.
For depending on the biological active matters such as enzyme or the antibody of dopamine specific recognition in the detection method of dopamine more
Matter prepares biosensor, and other than expensive, there are also other deficiencies, by taking enzyme as an example, in storage and use process
Temperature pH value of environment etc. all seriously affects its bioactivity, this just influences whether its application.Selection non-enzymatic,
Cheap there is the substance of preferable catalytic activity to prepare dopamine electrochemical sensor dopamine to be of great significance.
Summary of the invention
In order to solve shortcoming and defect present in existing dopamine detection technique, the primary purpose of the present invention is that providing
A kind of Dopamine Sensor based on sulfonated graphene supported palladium with excellent sensitivity and stability.
Another object of the present invention is to provide the preparations of the above-mentioned Dopamine Sensor based on sulfonated graphene supported palladium
Method.
A further object of the present invention is to provide the above-mentioned Dopamine Sensors based on sulfonated graphene supported palladium in DOPA
Application in amine detection.
The object of the invention is achieved through the following technical solutions：
A kind of Dopamine Sensor based on sulfonated graphene supported palladium, by reference electrode, to the work after electrode and modification
Make electrode composition, the working electrode after the modification is by working electrode and is solidificated in the material identification film group of working electrode surface
At, wherein the material identification film is mainly by sulfonated graphene load palladium composite material (Pd-SGN) and perfluorinated sulfonic resin
(Nafion) it is prepared；
The sulfonated graphene load palladium composite material is prepared by the following method：
A) it disperses graphene in water, obtains graphene dispersing solution；Using Diazosalt of sulfanilic acid to dispersion liquid
Middle graphene carries out sulfonation processing, obtains sulfonated graphene；
B) in water, sulfonated graphene is mixed with sodium citrate, is reacted in 80~110 DEG C, adjusts the pH of solution into
Property, it is centrifuged, washs, it is dry, obtain full reduction sulfonated graphene；
C) full reduction sulfonated graphene is dispersed in water, obtains full reduction sulfonated graphene dispersion liquid；Palladium chemical combination will be contained
Object and sodium citrate are mixed in water, are stirred, and palladium-containing solution is obtained；It is molten containing palladium that the addition of sulfonated graphene dispersant liquid drop will be restored entirely
It in liquid, is sufficiently stirred, obtains mixed liquor；The containing palladium compound is chlorine palladium acid or palladium chloride；
D) mixed liquor is mixed with reducing agent, is stirred to react under condition of ice bath, stood, adjusting pH value of solution to 1.7-2.3, after
It is continuous to be stirred to react, it filters, washs, it is dry, it obtains sulfonated graphene and loads palladium composite material.
The concentration of graphene dispersing solution is 1-10mg/mL in step a)；The Diazosalt of sulfanilic acid and graphene
Molal weight ratio be (0.5~2.9) mmol：100mg；The condition of sulfonation processing be stirred to react 1 under condition of ice bath~
5h；
Reaction product is centrifuged after sulfonation processing in step a), is washed.The washing refers to using distillation water-ethanol-
Distilled water is successively washed.
Diazosalt of sulfanilic acid is to obtain by the following method in step a)：184mg p-aminobenzene sulfonic acid, 72mg are sub-
Sodium nitrate, 30-100mL water and 1-6g 1mol/L hydrochloric acid or sulfuric acid are reacted under condition of ice bath, and acquisition contains p-aminophenyl
The solution of sulfonic acid diazonium salt.
The mass ratio of sodium citrate described in step b) and sulfonated graphene is (10-40)：1；The time of the reaction is 8
~12h；The pH for adjusting solution refers to be adjusted using sodium carbonate liquor；
Washing described in step b) refers to successively with distillation water-ethanol-distillation water washing；The drying is freeze-drying.
Sulfonated graphene mixed with sodium citrate described in step b) specifically refer to by sulfonated graphene ultrasonic disperse in
In water, the dispersion liquid of sulfonated graphene is obtained；Sodium citrate is soluble in water, obtain sodium citrate solution；Sodium citrate is molten
Liquid is added in sulfonated graphene dispersion liquid.
The concentration of the dispersion liquid of the sulfonated graphene is 1-5mg/mL；Sodium citrate and water in the sodium citrate solution
Mass volume ratio be 2g：5mL.
The quality molar ratio for restoring sulfonated graphene and containing palladium compound described in step c) entirely is (40~100) mg:
(0.1~5) mmol；The containing palladium compound and the molar ratio of sodium citrate are 1：(1~2).
The time of stirring described in step c) is 20~60min；The time being sufficiently stirred is 15~30h.
Containing palladium compound described in step c) is added in form of an aqueous solutions, and the concentration of containing palladium compound solution is
20mmol/L；The sodium citrate is added in form of an aqueous solutions, and sodium citrate solution concentration is 12.5mmol/L；Chemical combination containing palladium
Object solution, sodium citrate solution and water mixing, stirring obtain palladium-containing solution.
The molar ratio of containing palladium compound is (2~5) in reducing agent described in step d) and mixed liquor:1.
The reducing agent is sodium borohydride；The reducing agent is added as a solution, and the concentration of solution is 0.1mol/L；
The time being stirred to react is 2~6h；The standing refers to that room temperature stands 2~6h；The adjusting pH value of solution is
Refer to and is adjusted using hydrochloric acid；It is described to continue the time being stirred to react as 0.5~3h.
The drying is vacuum drying, and dry temperature is 60~100 DEG C.
The above-mentioned preparation method based on sulfonated graphene supported palladium Dopamine Sensor, including following preparation step：
(1) surface preparation is carried out to basal electrode；
(2) it disperses sulfonated graphene load palladium composite material in perfluor sulfoacid resin solution, obtains dispersion liquid；It adjusts
The pH of perfluor sulfoacid resin solution obtains neutral perfluor sulfoacid resin solution to neutrality；By dispersion liquid and neutral perfluorinated sulfonic acid tree
Lipoprotein solution is uniformly mixed to obtain composite solution；
(3) composite solution is added drop-wise to the electrode surface of step (1), room temperature is dried, and obtains loading based on sulfonated graphene
The modification working electrode of palladium；
(4) working electrode and reference electrode will be modified and three-electrode system is formed to electrode, and obtain the nothing of detection dopamine
Enzyme sensor is based on sulfonated graphene supported palladium Dopamine Sensor.
Surface preparation described in step (1) specifically refers to：By the surface of basal electrode successively use diameter be 0.3 μm and
0.05 μm of Al2O3Powder is polished to mirror surface, then is rinsed with water；Then successively it is cleaned by ultrasonic in dehydrated alcohol and water, takes out and use
Water is cleaned, and is dried.
Sulfonated graphene described in step (2) loads palladium composite material at perfluorosulfonic acid type resin solution (Nafion solution)
In concentration be 2.5~15mg/mL；Perfluor sulfoacid resin solution is to be diluted to 5% perfluor sulfoacid resin solution with ethyl alcohol
0.5~1%.
Neutrality perfluor sulfoacid resin solution described in step (2) is to dilute 5% perfluor sulfoacid resin solution with ethyl alcohol
To 0.5~1%, it is neutral for adjusting pH value of solution with highly basic.
The volume ratio of dispersion liquid described in step (2) and neutral perfluor sulfoacid resin solution is (1~3)：1.
Composite solution dripping quantity described in step (3) is 3~10 μ L.
Application of the above-mentioned Dopamine Sensor based on palladium load sulfonated graphene in dopamine detection.
The graphene that the present invention selects is a kind of Carbon Materials with unique netted lattice structure feature, has good conduction
Property, high mechanical strength, high-specific surface area, be easy to the advantages that functionalization, but its hydrophily is poor, is easy coagulation, it is difficult to disperse.This
The good sulfonic acid group of hydrophily is introduced into graphene by invention is conducive to improve its hydrophily, make its aqueous solution or other have
More preferably disperse in solvent, further shows its excellent physicochemical properties.The present invention selects palladium to be catalyzed as dopamine
Environmental condition influences its catalytic activity when agent can be to avoid using bioactive substances such as enzymes as catalyst.The present invention is with sulfonation stone
Black alkene is carrier, and palladium is catalyst preparation Electrochemical Modification electrode, is conducive to enhance catalyst loading, increases urging for modified electrode
Change performance, to construct the superior dopamine electrochemical sensor of performance.
The principle of the present invention：
The present invention is to prepare sulfonated graphene load palladium composite material first, and the composite material is by the good of sulfonic acid group
Hydrophily overcomes the shortcomings of that graphene hydrophily itself is poor, is easy coagulation and is difficult to disperse, and using the excellent electricity of palladium and urges
Change characteristic, combines both the electric conductivity and catalytic of enhancing composite material.Then, the film forming of perfluorinated sulfonic resin is utilized
Property, increase catalyst in the fixed amount and stability of electrode surface, in favor of the catalysis to substrate；Finally, taking appropriate mixed liquor
It drips in the working electrode on the working electrode of surface preparation, after being modified；Work electricity after recycling the modification
Pole, cooperation reference electrode with to electrode form three-electrode system, be made it is a kind of detection dopamine without enzyme electrochemical sensor.
The present invention by sulfonated graphene load palladium composite material applied to no enzyme electrochemical sensor, the detection being prepared
The sensor detection performance of dopamine is good, and detection range is 2.5 × 10-5~5.5 × 10-4Mol/L is catalyzed the response of reaction
Electric current and dopamine concentration variation are in a linear relationship, and the relationship of response current and dopamine concentration is I (A)=- 7.271 × 10-5-
3.661×10-4C (mmol/L), related coefficient R2=0.991, detection is limited to 1.31 × 10-5Mol/L (S/N=3), sensitivity
For 52.30mA/molcm2。
Preparation method of the invention and obtained product has the following advantages that and beneficial effect：
(1) detection dopamine of the present invention has good electron transmission without enzyme electrochemical sensor, can incite somebody to action
The electronics that reaction generates carries out good transfer, is able to achieve the detection of dopamine, improves the reaction speed of the sensor.
(2) detection dopamine of the present invention has good reproducibility and stability without enzyme electrochemical sensor,
Dopamine can accurately be detected, strong antijamming capability.
(3) detection that can be used for dopamine in serum without enzyme electrochemical sensor of detection dopamine of the present invention,
Preparation is simple, has wider detection range, lower detection limit, and reaction carries out under room temperature environment, and performance is stablized, and has good
Good application prospect.
Detailed description of the invention
Fig. 1 is the Dopamine Sensor based on sulfonated graphene supported palladium of the preparation of embodiment 2 in phosphate buffer solution
Cyclic voltammogram after the dopamine of various concentration is added dropwise is dense for the addition of dopamine in phosphate buffer solution in box in figure
Degree；
Fig. 2 is the Dopamine Sensor based on sulfonated graphene supported palladium of the preparation of embodiment 2 in phosphate buffer solution
The linear relationship chart after the dopamine of various concentration between the response current generated and various concentration dopamine is added dropwise.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of the dopamine electrochemical sensor based on sulfonated graphene supported palladium, includes the following steps：
(1) be successively with diameter by the glass-carbon electrode that diameter is 3mm 0.3 μm and 0.05 μm Al2O3Powder is polished to mirror
Then face is successively cleaned by ultrasonic 1min with distilled water flushing in dehydrated alcohol and distilled water, take out and use distilled water flushing, room
Temperature dries to obtain pretreated glass-carbon electrode.
(2) preparation of sulfonated graphene load palladium composite material：
(2-1) is dispersed graphene in water, obtains graphene dispersing solution, concentration 2mg/mL；It is added into reaction vessel
184mg p-aminobenzene sulfonic acid and 72mg sodium nitrite are added 40mL distilled water and 2g 1mol/L hydrochloric acid, stir in ice bath pot
30min is reacted, the solution containing Diazosalt of sulfanilic acid is obtained；
The solution of (2-2) containing Diazosalt of sulfanilic acid is added in the graphene dispersing solution of 50mL, p-aminophenyl sulphur
The molal weight of sour diazonium salt and graphene ratio is 1.06mmol：100mg is stirred to react 2h under condition of ice bath, with 4000rpm's
Revolving speed centrifugation is washed repeatedly according to distillation water-ethanol-distilled water sequence, obtains sulfonated graphene；
(2-3) by sulfonated graphene ultrasonic disperse in water, ultrasonic disperse 30min obtains sulfonated graphene solution, concentration
For 1.6mg/mL；2g sodium citrate is dissolved with 5mL distilled water, obtains sodium citrate solution；Sodium citrate solution is added to
In 100mL sulfonated graphene solution, the mass ratio of sodium citrate and sulfonated graphene is 12.5：10h is reacted in 1,90 DEG C of oil bath, instead
After the completion of answering, 2~4 drop 5%Na are added2CO3, then it is centrifuged with the centrifuge that revolving speed is 4000rpm, with distillation water-ethanol-steaming
The sequence of distilled water carries out being centrifuged repeatedly washing operation, and full reduction sulfonated graphene is made in freeze-drying afterwards for 24 hours；
50mg is restored sulfonated graphene entirely and is configured to the sulfonation that concentration is 5mg/mL with distilled water ultrasonic disperse 2h by (2-4)
Graphene dispersing solution；By 10.10mL 20mmol/L chlorine palladium acid, 16.16mL12.5mmol/L sodium citrate solution and 23.74mL
Distilled water (total solution volume is 50mL after chlorine palladium acid solution and citric acid solution is added), stirs 30min, chlorine palladium acid and citric acid
The molar ratio of sodium is 1：1, obtain mixed liquor；Sulfonated graphene dispersion liquid is added dropwise in mixed liquor, water is subsequently placed at
Bath, stirring at normal temperature is overnight, obtains the dispersion liquid that palladium load capacity is 30wt%；The sodium borohydride that 5.096mL 0.1mol/L is added is molten
Liquid places it in ice bath pot and is stirred to react 2h, to which after the reaction was completed, room temperature stands 2h；With 0.1mol/L hydrochloric acid by solution
After pH is adjusted to 2, it is stirred to react 1h, uses distilled water filtering and washing after the reaction was completed, is placed in 60 DEG C of vacuum ovens dry 8h, system
It obtains sulfonated graphene and loads palladium composite material；
(3) perfluor sulfoacid resin solution (5% Du Pont's Nafion solution is dispersed by sulfonated graphene load palladium composite material
0.8% solution is diluted to ethyl alcohol) in, dispersion liquid is obtained, the concentration of dispersion liquid is 2.5mg/mL；By 5% Du Pont Nafion
Solution is diluted to 0.8% solution with ethyl alcohol, adjusts perfluor sulfoacid resin solution to neutrality using 0.1mol/L NaOH solution,
Obtain neutral solution；Dispersion liquid is mixed in equal volume with neutral solution, obtains composite solution；Take 5 μ L composite solutions drop in step
(1) electrode surface, dries at room temperature, obtains the modification working electrode based on sulfonated graphene supported palladium；
(4) will modification working electrode and reference electrode and to electrode composition three-electrode system (platinum electrode be to electrode, silver/
Silver chlorate is reference electrode), obtain detection dopamine without enzyme electrochemical sensor i.e. based on the more of sulfonated graphene supported palladium
Bar amine electrochemical sensor.
Electrochemical test is carried out at room temperature, is carried out in 10mL phosphate buffer solution (0.1mol/L, pH 6.0), is surveyed
Logical N before examination2, cyclic voltammetry is used in test process.Wherein dopamine solution is not added dropwise for blank control, drips after stable testing
Add 300 μ L dopamine solutions.
For the present embodiment when dopamine concentration is 0.15mmol/L, the oxidation peak catalytic current of test is 7.072 × 10-5A,
The reduction peak catalytic current of test is 9.817 × 10-5A。
Embodiment 2
A kind of preparation method of the dopamine electrochemical sensor based on sulfonated graphene supported palladium, includes the following steps：
(1) be successively with diameter by the glass-carbon electrode that diameter is 3mm 0.3 μm and 0.05 μm Al2O3Powder is polished to mirror
Then face is successively cleaned by ultrasonic 1min with distilled water flushing in dehydrated alcohol and distilled water, take out and use distilled water flushing, room
Temperature dries to obtain pretreated glass-carbon electrode；
(2) preparation of sulfonated graphene load palladium composite material：
(2-1) is dispersed graphene in water, obtains graphene dispersing solution, concentration 1mg/mL；It is added into reaction vessel
184mg p-aminobenzene sulfonic acid and 72mg sodium nitrite are added 40mL distilled water and 2g 1mol/L hydrochloric acid, stir in ice bath pot
30min is reacted, the solution containing Diazosalt of sulfanilic acid is obtained；
The solution of (2-2) containing Diazosalt of sulfanilic acid is added in the graphene dispersing solution of 100mL, p-aminophenyl sulphur
The molal weight of sour diazonium salt and graphene ratio is 1.06mmol：100mg is stirred to react 2h under condition of ice bath, with 4000rpm's
Revolving speed centrifugation is washed repeatedly according to distillation water-ethanol-distilled water sequence, obtains sulfonated graphene；
(2-3) by sulfonated graphene ultrasonic disperse in water, ultrasonic disperse 30min obtains sulfonated graphene solution, concentration
For 1.6mg/mL；2g sodium citrate is dissolved with 5mL distilled water, obtains sodium citrate solution；Sodium citrate solution is added to
In 100mL sulfonated graphene solution, the mass ratio of sodium citrate and sulfonated graphene is 12.5：10h is reacted in 1,90 DEG C of oil bath, instead
After the completion of answering, 2~4 drop 5%Na are added2CO3, then it is centrifuged with the centrifuge that revolving speed is 4000rpm, with distillation water-ethanol-steaming
The sequence of distilled water carries out being centrifuged repeatedly washing operation, and full reduction sulfonated graphene is made in freeze-drying afterwards for 24 hours；
50mg is restored sulfonated graphene entirely and is configured to the sulfonation that concentration is 5mg/mL with distilled water ultrasonic disperse 2h by (2-4)
Graphene dispersing solution；By 15.7mL 20mmol/L chlorine palladium acid, 25.1mL 12.5mmol/L sodium citrate solution and 9.2mL distillation
Water (total solution volume is 50mL after chlorine palladium acid solution and citric acid solution is added), stirring 30min, chlorine palladium acid and sodium citrate
Molar ratio is 1：1, obtain mixed liquor；Sulfonated graphene dispersion liquid is added dropwise in mixed liquor, water-bath is subsequently placed at,
Stirring at normal temperature is stayed overnight, and the dispersion liquid that palladium load capacity is 40wt% is obtained；The sodium borohydride solution of 7.924mL 0.1mol/L is added, it will
It is placed in ice bath pot and is stirred to react 2h, to which after the reaction was completed, room temperature stands 2h；The pH of solution is adjusted to 0.1mol/L hydrochloric acid
After 2, it is stirred to react 1h, uses distilled water filtering and washing after the reaction was completed, dry 8h is placed in 60 DEG C of vacuum ovens, sulfonation is made
Graphene-supported palladium composite material；
(3) perfluor sulfoacid resin solution (5% Du Pont's Nafion solution is dispersed by sulfonated graphene load palladium composite material
0.8% solution is diluted to ethyl alcohol) in, dispersion liquid is obtained, the concentration of dispersion liquid is 5mg/mL；5% Du Pont's Nafion solution
It is diluted to 0.8% solution with ethyl alcohol, perfluor sulfoacid resin solution is adjusted to neutrality using 0.1mol/L NaOH solution, is obtained
Neutral solution；By dispersion liquid with neutral solution to mix in equal volume, composite solution is obtained；Take 5 μ L composite solutions drop in step (1)
Electrode surface, dry at room temperature, obtain the modification working electrode based on sulfonated graphene supported palladium；
(4) by after modification working electrode and reference electrode and to electrode composition three-electrode system (platinum electrode be to electrode,
Silver/silver chlorate be reference electrode), obtain detection dopamine without enzyme sensor.
Electrochemical test is carried out at room temperature, is carried out in 10mL phosphate buffer solution (0.1mol/L, pH 6.0), is surveyed
Logical N before examination2, cyclic voltammetry is used in test process.Wherein dopamine solution is not added dropwise for blank control, drips after stable testing
Add 300 μ L dopamine solutions.
For the present embodiment when dopamine concentration is 0.15mmol/L, the oxidation peak catalytic current of test is 8.423 × 10-5A,
The reduction peak catalytic current of test is 1.1095 × 10-5A。
Dopamine Sensor manufactured in the present embodiment based on the sulfonated graphene supported palladium that palladium carrying capacity is 40wt% (is based on
The Dopamine Sensor of sulfonated graphene supported palladium) various concentration is added dropwise in phosphate buffer solution (0.1mo1/L, pH 6.0)
Dopamine after cyclic voltammogram as shown in Figure 1, in buffer solution dopamine concentration increase, catalytic current increase.Its
The dopamine concentration that middle redox curve right end is corresponding in turn to from top to bottom be 0.0256mmo1/L, 0.0761mmo1/L,
0.15mmo1/L、0.245mmo1/L、0.337mmo1/L、0.425mmo1/L、0.467mmo1/L、0.55mmo1/L、
0.631mmo1/L,0.708mmo1/L,0.783mmo1/L,0.855mmo1/L,0.924mmo1/L.Sulfonated graphene is utilized
The electric conductivity and catalytic of composite material supported palladium and the film forming of perfluorinated sulfonic resin increase catalyst in electrode surface
Fixed amount and stability realize effective catalysis to substrate.
Dopamine Sensor manufactured in the present embodiment based on sulfonated graphene supported palladium is added dropwise in phosphate buffer solution
Linear relationship chart between the response current generated after the dopamine of various concentration and various concentration dopamine is as shown in Figure 2.It should
Modified electrode is 2.5 × 10 to substrate detection range-5~5.5 × 10-4The relationship of mol/L, response current and dopamine concentration is
I (A)=- 7.271 × 10-5-3.661×10-4C (mmol/L), related coefficient R2=0.991, detection is limited to 1.31 × 10- 5Mol/L (S/N=3), sensitivity 52.30mAmol-1cm-2。
Embodiment 3
A kind of preparation method of the dopamine electrochemical sensor based on sulfonated graphene supported palladium, includes the following steps：
(1) be successively with diameter by the glass-carbon electrode that diameter is 3mm 0.3 μm and 0.05 μm Al2O3Powder is polished to mirror
Then face is successively cleaned by ultrasonic 1min with distilled water flushing in dehydrated alcohol and distilled water, take out and use distilled water flushing, room
Temperature dries to obtain pretreated glass-carbon electrode；
(2) preparation of sulfonated graphene load palladium composite material：
(2-1) is dispersed graphene in water, obtains graphene dispersing solution, concentration 1mg/mL；It is added into reaction vessel
184mg p-aminobenzene sulfonic acid and 72mg sodium nitrite are added 40mL distilled water and 2g 1mol/L hydrochloric acid, stir in ice bath pot
30min is reacted, the solution containing Diazosalt of sulfanilic acid is obtained；
The solution of (2-2) containing Diazosalt of sulfanilic acid is added in the graphene dispersing solution of 100mL, p-aminophenyl sulphur
The molal weight of sour diazonium salt and graphene ratio is 1.06mmol：100mg is stirred to react 2h under condition of ice bath, with 4000rpm's
Revolving speed centrifugation is washed repeatedly according to distillation water-ethanol-distilled water sequence, obtains sulfonated graphene；
(2-3) by sulfonated graphene ultrasonic disperse in water, ultrasonic disperse 30min obtains sulfonated graphene solution, concentration
For 1.6mg/mL；2g sodium citrate is dissolved with 5mL distilled water, obtains sodium citrate solution；Sodium citrate solution is added to
In 100mL sulfonated graphene solution, the mass ratio of sodium citrate and sulfonated graphene is 12.5：10h is reacted in 1,90 DEG C of oil bath, instead
After the completion of answering, 2~4 drop 5%Na are added2CO3, then it is centrifuged with the centrifuge that revolving speed is 4000rpm, with distillation water-ethanol-steaming
The sequence of distilled water carries out being centrifuged repeatedly washing operation, and full reduction sulfonated graphene is made in freeze-drying afterwards for 24 hours；
50mg is restored sulfonated graphene entirely and is configured to the sulfonation that concentration is 5mg/mL with distilled water ultrasonic disperse 2h by (2-4)
Graphene dispersing solution；By 15.7mL 20mmol/L chlorine palladium acid, 25.1mL 12.5mmol/L sodium citrate solution and 9.2mL distillation
Water (total solution volume is 50mL after chlorine palladium acid solution and citric acid solution is added), stirring 30min, chlorine palladium acid and sodium citrate
Molar ratio is 1：1, obtain mixed liquor；Sulfonated graphene dispersion liquid is added dropwise in mixed liquor, water-bath is subsequently placed at,
Stirring at normal temperature is stayed overnight, and the dispersion liquid that palladium load capacity is 40wt% is obtained；The sodium borohydride solution of 7.924mL 0.1mol/L is added, it will
It is placed in ice bath pot and is stirred to react 2h, to which after the reaction was completed, room temperature stands 2h；The pH of solution is adjusted to 0.1mol/L hydrochloric acid
After 2, it is stirred to react 1h, uses distilled water filtering and washing after the reaction was completed, dry 8h is placed in 60 DEG C of vacuum ovens, sulfonation is made
Graphene-supported palladium composite material；
(3) perfluor sulfoacid resin solution (5% Du Pont's Nafion solution is dispersed by sulfonated graphene load palladium composite material
0.8% solution is diluted to ethyl alcohol) in, dispersion liquid is obtained, the concentration of dispersion liquid is 7.5mg/mL；5% Du Pont Nafion is molten
Liquid is diluted to 0.8% solution with ethyl alcohol, adjusts perfluor sulfoacid resin solution to neutrality using 0.1mol/L NaOH solution, obtains
Obtain neutral solution；By dispersion liquid with neutral solution to mix in equal volume, composite solution is obtained；Take 5 μ L composite solutions drop in step
(1) electrode surface, dries at room temperature, obtains the modification working electrode based on sulfonated graphene supported palladium；
(4) by after the modification working electrode and reference electrode and to electrode composition three-electrode system (platinum electrode be pair
Electrode, silver/silver chlorate be reference electrode), obtain detection dopamine without enzyme sensor.
Electrochemical test is carried out at room temperature, is carried out in 10mL phosphate buffer solution (0.1mol/L, pH 6.0), is surveyed
Logical N before examination2, cyclic voltammetry is used in test process.Wherein dopamine solution is not added dropwise for blank control, drips after stable testing
Add 300 μ L dopamine solutions.
For the present embodiment when dopamine concentration is 0.15mmol/L, the oxidation peak catalytic current of test is 7.5455 × 10- 5A, the reduction peak catalytic current of test are 9.725 × 10-5A。
Embodiment 4
A kind of preparation method of the dopamine electrochemical sensor based on sulfonated graphene supported palladium, includes the following steps：
(1) be successively with diameter by the glass-carbon electrode that diameter is 3mm 0.3 μm and 0.05 μm Al2O3Powder is polished to mirror
Then face is successively cleaned by ultrasonic 1min with distilled water flushing in dehydrated alcohol and distilled water, take out and use distilled water flushing, room
Temperature dries to obtain pretreated glass-carbon electrode.
(2) preparation of sulfonated graphene load palladium composite material：
(2-1) is dispersed graphene in water, obtains graphene dispersing solution, concentration 1mg/mL；It is added into reaction vessel
184mg p-aminobenzene sulfonic acid and 72mg sodium nitrite are added 40mL distilled water and 2g 1mol/L hydrochloric acid, stir in ice bath pot
30min is reacted, the solution containing Diazosalt of sulfanilic acid is obtained；
The solution of (2-2) containing Diazosalt of sulfanilic acid is added in the graphene dispersing solution of 100mL, p-aminophenyl sulphur
The molal weight of sour diazonium salt and graphene ratio is 1.06mmol：100mg is stirred to react 2h under condition of ice bath, with 4000rpm's
Revolving speed centrifugation is washed repeatedly according to distillation water-ethanol-distilled water sequence, obtains sulfonated graphene；
(2-3) by sulfonated graphene ultrasonic disperse in water, ultrasonic disperse 30min obtains sulfonated graphene solution, concentration
For 1.6mg/mL；2g sodium citrate is dissolved with 5mL distilled water, obtains sodium citrate solution；Sodium citrate solution is added to
In 100mL sulfonated graphene solution, the mass ratio of sodium citrate and sulfonated graphene is 12.5：10h is reacted in 1,90 DEG C of oil bath, instead
After the completion of answering, 2~4 drop 5%Na are added2CO3, then it is centrifuged with the centrifuge that revolving speed is 4000rpm, with distillation water-ethanol-steaming
The sequence of distilled water carries out being centrifuged repeatedly washing operation, and full reduction sulfonated graphene is made in freeze-drying afterwards for 24 hours；
50mg is restored sulfonated graphene entirely and is configured to the sulfonation that concentration is 5mg/mL with distilled water ultrasonic disperse 2h by (2-4)
Graphene dispersing solution；By 15.7mL 20mmol/L chlorine palladium acid, 25.1mL 12.5mmol/L sodium citrate solution and 9.2mL distillation
Water (total solution volume is 50mL after chlorine palladium acid solution and citric acid solution is added), stirring 30min, chlorine palladium acid and sodium citrate
Molar ratio is 1：1, obtain mixed liquor；Sulfonated graphene dispersion liquid is added dropwise in mixed liquor, water-bath is subsequently placed at,
Stirring at normal temperature is stayed overnight, and the dispersion liquid that palladium load capacity is 40wt% is obtained；The sodium borohydride solution of 7.924mL 0.1mol/L is added, it will
It is placed in ice bath pot and is stirred to react 2h, to which after the reaction was completed, room temperature stands 2h；The pH of solution is adjusted to 0.1mol/L hydrochloric acid
After 2, it is stirred to react 1h, uses distilled water filtering and washing after the reaction was completed, dry 8h is placed in 60 DEG C of vacuum ovens, sulfonation is made
Graphene-supported palladium composite material；
(3) perfluor sulfoacid resin solution (5% Du Pont's Nafion solution is dispersed by sulfonated graphene load palladium composite material
0.8% solution is diluted to ethyl alcohol) in, dispersion liquid is obtained, the concentration of dispersion liquid is 10mg/mL；5% Du Pont's Nafion solution
It is diluted to 0.8% solution with ethyl alcohol, perfluor sulfoacid resin solution is adjusted to neutrality using 0.1mol/L NaOH solution, is obtained
Neutral solution；By dispersion liquid with neutral solution to mix in equal volume, composite solution is obtained；Take 5 μ L composite solutions drop in step (1)
Electrode surface, dry at room temperature, obtain the modification working electrode based on sulfonated graphene supported palladium；
(4) by after modification working electrode and reference electrode and to electrode composition three-electrode system (platinum electrode be to electrode,
Silver/silver chlorate be reference electrode), obtain detection dopamine without enzyme sensor.
Electrochemical test is carried out at room temperature, is carried out in 10mL phosphate buffer solution (0.1mol/L, pH 6.0), is surveyed
Logical N before examination2, cyclic voltammetry is used in test process.Wherein dopamine solution is not added dropwise for blank control, drips after stable testing
Add 300 μ L dopamine solutions.
For the present embodiment when dopamine concentration is 0.15mmol/L, the oxidation peak catalytic current of test is 7.334 × 10-5A,
The reduction peak catalytic current of test is 8.571 × 10-5A。
Embodiment 5
A kind of preparation method of the dopamine electrochemical sensor based on sulfonated graphene supported palladium, includes the following steps：
(1) be successively with diameter by the glass-carbon electrode that diameter is 3mm 0.3 μm and 0.05 μm Al2O3Powder is polished to mirror
Then face is successively cleaned by ultrasonic 1min with distilled water flushing in dehydrated alcohol and distilled water, take out and use distilled water flushing, room
Temperature dries to obtain pretreated glass-carbon electrode；
(2) preparation of sulfonated graphene load palladium composite material：
(2-1) is dispersed graphene in water, obtains graphene dispersing solution, concentration 1mg/mL；It is added into reaction vessel
184mg p-aminobenzene sulfonic acid and 72mg sodium nitrite are added 40mL distilled water and 2g 1mol/L hydrochloric acid, stir in ice bath pot
30min is reacted, the solution containing Diazosalt of sulfanilic acid is obtained；
The solution of (2-2) containing Diazosalt of sulfanilic acid is added in the graphene dispersing solution of 100mL, p-aminophenyl sulphur
The molal weight of sour diazonium salt and graphene ratio is 1.06mmol：100mg is stirred to react 2h under condition of ice bath, with 4000rpm's
Revolving speed centrifugation is washed repeatedly according to distillation water-ethanol-distilled water sequence, obtains sulfonated graphene；
(2-3) by sulfonated graphene ultrasonic disperse in water, ultrasonic disperse 30min obtains sulfonated graphene solution, concentration
For 1.6mg/mL；2g sodium citrate is dissolved with 5mL distilled water, obtains sodium citrate solution；Sodium citrate solution is added to
In 100mL sulfonated graphene solution, the mass ratio of sodium citrate and sulfonated graphene is 12.5：10h is reacted in 1,90 DEG C of oil bath, instead
After the completion of answering, 2~4 drop 5%Na are added2CO3, then it is centrifuged with the centrifuge that revolving speed is 4000rpm, with distillation water-ethanol-steaming
The sequence of distilled water carries out being centrifuged repeatedly washing operation, and full reduction sulfonated graphene is made in freeze-drying afterwards for 24 hours；
50mg is restored sulfonated graphene entirely and is configured to the sulfonation that concentration is 5mg/mL with distilled water ultrasonic disperse 2h by (2-4)
Graphene dispersing solution；By 15.7mL 20mmol/L chlorine palladium acid, 25.1mL 12.5mmol/L sodium citrate solution and 9.2mL distillation
Water (total solution volume is 50mL after chlorine palladium acid solution and citric acid solution is added), stirring 30min, chlorine palladium acid and sodium citrate
Molar ratio is 1：1, obtain mixed liquor；Sulfonated graphene dispersion liquid is added dropwise in mixed liquor, water-bath is subsequently placed at,
Stirring at normal temperature is stayed overnight, and the dispersion liquid that palladium load capacity is 40wt% is obtained；The sodium borohydride solution of 7.924mL 0.1mol/L is added, it will
It is placed in ice bath pot and is stirred to react 2h, to which after the reaction was completed, room temperature stands 2h；The pH of solution is adjusted to 0.1mol/L hydrochloric acid
After 2, it is stirred to react 1h, uses distilled water filtering and washing after the reaction was completed, dry 8h is placed in 60 DEG C of vacuum ovens, sulfonation is made
Graphene-supported palladium composite material；
(3) perfluor sulfoacid resin solution (5% Du Pont's Nafion solution is dispersed by sulfonated graphene load palladium composite material
0.8% solution is diluted to ethyl alcohol) in, dispersion liquid is obtained, the concentration of dispersion liquid is 12.5mg/mL；5% Du Pont Nafion is molten
Liquid is diluted to 0.8% solution with ethyl alcohol, adjusts perfluor sulfoacid resin solution to neutrality using 0.1mol/L NaOH solution, obtains
Obtain neutral solution；By dispersion liquid with neutral solution to mix in equal volume, composite solution is obtained；Take 5 μ L composite solutions drop in step
(1) electrode surface, dries at room temperature, obtains the modification working electrode based on sulfonated graphene supported palladium；
(4) by after modification working electrode and reference electrode and to electrode composition three-electrode system (platinum electrode be to electrode,
Silver/silver chlorate be reference electrode), obtain detection dopamine without enzyme sensor.
Electrochemical test is carried out at room temperature, is carried out in 10mL phosphate buffer solution (0.1mol/L, pH 6.0), is surveyed
Logical N before examination2, cyclic voltammetry is used in test process.Wherein dopamine solution is not added dropwise for blank control, drips after stable testing
Add 300 μ L dopamine solutions.
For the present embodiment when dopamine concentration is 0.15mmol/L, the oxidation peak catalytic current of test is 5.303 × 10-5A,
The reduction peak catalytic current of test is 6.281 × 10-5A。
The preparation process of the graphene is as follows：
(a) graphite powder is cleaned；
(b) graphite powder after taking cleaning, prepares graphene oxide using modified Hummers method；
(c) appropriate graphene oxide is taken, using reduction method, prepares graphene.
The operation of graphite powder cleaning process described in step (a) is as follows：2.5~10g graphite powder is weighed in large beaker, is added
100mL distilled water, then 100mL concentrated hydrochloric acid is added in ventilating kitchen, 2h is heated and stirred in 60~80 DEG C of water-baths, is filtered by vacuum
Afterwards, it is successively cleaned with distilled water, acetone, ethyl alcohol, after cleaning, 100 DEG C of drying in vacuum oven is put into, later with quartz
Mortar grinder powdering is spare.
The process of graphene oxide preparation manipulation described in step (b) is as follows：(1) low-temp reaction (0~4 DEG C)：In ice-water bath
In be put into 1000mL large beaker, add the dense H of 110mL2SO4, while stirring so that its temperature is down to low-temp reaction section, then according to
It is secondary that cleaned 2.5~10g graphite powder, 2.5g NaNO is added3, 15g KMnO4.Rear timing is added, 90min is stirred to react,
Solution is in purple green；(2) medium temperature reaction (30~40 DEG C)：Temperature is increased, its temperature is made to be maintained at 35 DEG C or so under stiring,
Clock reaction 90min, solution are still in purple green；(3) pyroreaction (70~100 DEG C)：After medium temperature reaction, slowly into beaker
220mL deionized water is added, then heats and controls temperature at 85 DEG C, being then slowly added to a certain amount of hydrogen peroxide, (5% about
13mL) golden yellow is gradually become to solution；(4) after completion of the reaction to the preparation, when taking advantage of reaction solution warm, after reaction
Solution be washed with deionized and filter, and be centrifuged repeatedly with the centrifuge that revolving speed is 4000rpm and clean filtering again, until filter
It can't detect SO in liquid4 2-Until (use BaCl2It examines).Obtained black product deionized water is cleaned by ultrasonic simultaneously at this time
Hygrometric state graphite oxide is obtained after centrifugation.
The process of graphene preparation manipulation described in step (c) is as follows：(1) prereduction：Weigh 4-8g hygrometric state graphite oxide in
In conical flask, distilled water is added, 1g/mL graphite oxide solution is made；Use 5%Na2CO3Adjust graphite oxide solution pH be 9~
After the completion of ultrasonic, the reducing agents such as sodium borohydride, hydrazine hydrate or vitamin C, reducing agent and oxidation stone is added in 10, ultrasonic disperse 3h
The mass ratio of black alkene is (1-2):1, it is subsequently placed in 80 DEG C of water bath with thermostatic control, stirs lower reaction 2h；To after the reaction was completed, carry out
Vacuum filtration.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of Dopamine Sensor based on sulfonated graphene supported palladium, it is characterised in that：By reference electrode, to electrode and repair
Working electrode composition after decorations, working electrode after the modification is by working electrode and is solidificated in the substance of working electrode surface and knows
Other film composition, wherein the material identification film mainly loads palladium composite material by sulfonated graphene and prepared by perfluorinated sulfonic resin
It forms；
The sulfonated graphene load palladium composite material is prepared by the following method：
A) it disperses graphene in water, obtains graphene dispersing solution；Using Diazosalt of sulfanilic acid to stone in dispersion liquid
Black alkene carries out sulfonation processing, obtains sulfonated graphene；
B) in water, sulfonated graphene is mixed with sodium citrate, is reacted in 80~110 DEG C, adjust the pH of solution to neutrality, from
The heart washs, dry, obtains full reduction sulfonated graphene；
C) sulfonated graphene ultrasonic disperse will be restored entirely in water, obtain full reduction sulfonated graphene dispersion liquid；Palladium chemical combination will be contained
Object and sodium citrate are mixed in water, are stirred, and palladium-containing solution is obtained；It is molten containing palladium that the addition of sulfonated graphene dispersant liquid drop will be restored entirely
It in liquid, is sufficiently stirred, obtains mixed liquor；The containing palladium compound is chlorine palladium acid or palladium chloride；
D) mixed liquor is mixed with reducing agent, is stirred to react under condition of ice bath, stood, adjusted pH value of solution to 1.7-2.3, continue to stir
Reaction is mixed, is filtered, is washed, it is dry, it obtains sulfonated graphene and loads palladium composite material.
2. the Dopamine Sensor according to claim 1 based on sulfonated graphene supported palladium, it is characterised in that：In step a)
The molal weight of the Diazosalt of sulfanilic acid and graphene ratio is (0.5~2.9) mmol：100mg；
The mass ratio of sodium citrate described in step b) and sulfonated graphene is (10-40)：1；
The quality molar ratio for restoring sulfonated graphene and containing palladium compound described in step c) entirely is (40~100) mg:(0.1~
5)mmol；The containing palladium compound and the molar ratio of sodium citrate are 1：(1~2)；
The molar ratio of containing palladium compound is (2~5) in reducing agent described in step d) and mixed liquor:1.
3. the Dopamine Sensor according to claim 1 based on sulfonated graphene supported palladium, it is characterised in that：In step d)
The reducing agent is sodium borohydride；The condition of the processing of sulfonation described in step a) is to be stirred to react 1~5h under condition of ice bath；
The time being stirred to react described in step d) is 2~6h；The standing refers to that room temperature stands 2~6h；Described in step d)
Continuing the time being stirred to react is 0.5~3h.
4. the Dopamine Sensor according to claim 1 based on sulfonated graphene supported palladium, it is characterised in that：
The concentration of graphene dispersing solution is 1-10mg/mL in step a)；
The time of reaction described in step b) is 8~12h；The pH that solution is adjusted described in step b) refers to using sodium carbonate liquor
It adjusts；
The time of stirring described in step c) is 20~60min；The time being sufficiently stirred is 15~30h；
Reducing agent described in step d) is added as a solution；
Adjusting pH value of solution described in step d) refers to be adjusted using hydrochloric acid.
5. the Dopamine Sensor according to claim 1 based on sulfonated graphene supported palladium, it is characterised in that：
Sulfonated graphene is mixed with sodium citrate described in step b) and is specifically referred to by sulfonated graphene ultrasonic disperse in water,
Obtain the dispersion liquid of sulfonated graphene；Sodium citrate is soluble in water, obtain sodium citrate solution；Sodium citrate solution is added
In sulfonated graphene dispersion liquid.
6. the preparation method of the Dopamine Sensor based on sulfonated graphene supported palladium described in any one according to claim 1~5,
It is characterized in that：Include the following steps：
(1) surface preparation is carried out to basal electrode；
(2) it disperses sulfonated graphene load palladium composite material in perfluor sulfoacid resin solution, obtains dispersion liquid；Adjust perfluor
The pH of sulfonate resin solution obtains neutral perfluor sulfoacid resin solution to neutrality；Dispersion liquid and neutral perfluorinated sulfonic resin is molten
Liquid is uniformly mixed to obtain composite solution；
(3) composite solution is added drop-wise to the electrode surface of step (1), room temperature is dried, and is obtained based on sulfonated graphene supported palladium
Modify working electrode；
(4) working electrode and reference electrode will be modified and three-electrode system is formed to electrode, and obtain passing without enzyme for detection dopamine
Sensor is based on sulfonated graphene supported palladium Dopamine Sensor.
7. the preparation method of the Dopamine Sensor according to claim 6 based on sulfonated graphene supported palladium, feature exist
In：
The volume ratio of dispersion liquid described in step (2) and neutral perfluor sulfoacid resin solution is (1~3)：1；
The concentration of sulfonated graphene load palladium composite material is 2.5~15mg/mL, dispersion liquid in dispersion liquid described in step (2)
The mass concentration of middle perfluor sulfoacid resin solution is 0.5~1%.
8. the preparation method of the Dopamine Sensor according to claim 6 based on sulfonated graphene supported palladium, feature exist
In：Neutrality perfluor sulfoacid resin solution described in step (2) is that 5% perfluor sulfoacid resin solution is diluted to 0.5 with ethyl alcohol
~1%, it is neutral for adjusting pH value of solution with highly basic.
9. the preparation method of the Dopamine Sensor according to claim 6 based on sulfonated graphene supported palladium, feature exist
In：Surface preparation described in step (1) specifically refers to：It is 0.3 μm and 0.05 μm that diameter is successively used on the surface of basal electrode
Al2O3Powder is polished to mirror surface, then is rinsed with water；Then successively it is cleaned by ultrasonic in dehydrated alcohol and water, taking-up is washed with water
Only, it dries.
10. the Dopamine Sensor based on sulfonated graphene supported palladium described in any one is examined in dopamine according to claim 1~5
Application in survey.
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