CN104820008B - A kind of preparation method of zinc oxide nano mitron/graphene composite film modified electrode - Google Patents
A kind of preparation method of zinc oxide nano mitron/graphene composite film modified electrode Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of zinc oxide nano mitron/graphene composite film modified electrode, high molecular polymer and salt compounds dissolving in organic solvent, are formed polymer solution by (1)；Above-mentioned polymer solution is spun into by nanofiber precursor using electrostatic spinning process；(2) above-mentioned nanofiber precursor is completed into oxidizing process in air atmosphere and obtains zinc oxide nano mitron；(3) nanotube Graphene complex liquid is obtained by Activated Graphite alkene particle and zinc oxide nano mitron are compound, and be coated on electrode and can obtain zinc-oxide nano pipe graphene composite film modified electrode.Obtained product of the invention is easy to make due to its, cost is relatively low, good stability, its electrode modified material zinc oxide nano mitron specific surface area is big, surface can be coordinated rich in hydroxyl with heavy metal ion, adsorb the Graphene on its surface and further increase its electric conductivity, thus there is sensitive response in trace heavy metal plumbum ion concentration in determining water body as sensing electrode.
Description
Technical field
The invention belongs to the preparation field of combination electrode, more particularly to a kind of zinc oxide nano mitron/graphene composite film is repaiied
Adorn the preparation method of electrode.
Background technology
Zinc oxide is a kind of important semi-conducting material, and due to its small size, high-specific surface area, many adsorption sites cause
Its surface can be with the increase of activity.Compared with other conventional semiconductor materials, due to being moved with luminous efficiency and electronics higher
Move speed and be applied to luminescent material and electronic device material.Due to its excellent electronic conduction ability and catalysis characteristics, closely
There is larger research in terms of electrochemical sensing over year.Simultaneously because zinc oxide surface contains more hydroxyl etc., system is commonly used to
The sorbing material of standby heavy metal ion.The preparation method of zinc oxide nano fiber generally has the precipitation method, hydro-thermal method, electrochemical deposition
Method, sol-gel process.But these methods are all different degrees of to be present, the product that such as prepared by the precipitation method has reunion existing
As requirement of the hydro-thermal method to experimental facilities is higher, although sol-gel process course of reaction is controllable, its cost of material is expensive.
And product prepared by these methods is mostly nano particle or nano thin-film.
Electrostatic spinning prepares micro-, nanofiber technology there is provided a kind of uniqueness, aperture, the hole of its gained electrospinning fibre
Gap rate can be controlled, and be usually applied to including organizational project, drug delivery, catalyst carrier, gas storage, sensor etc.
Many-side, is most economical, the easily method that prepare nanofiber of current most study.Oxygen is obtained using electrostatic spinning technique
Not only method is simple to operation to change zinc nanofiber, and specific surface area is big, porosity is high, homogeneous because the product for preparing has
Property good, easy film forming the advantages of, thus its product has repeatable utilization when combination electrode is made.
Bio-sensing research about zinc oxide modified electrode at present has Static Spinning ZnO/ carbon composite nano-fibers to modify electricity
Pole is used for the measure of trace lead, and (Zhou Xin, Yang Jianmao, Xin Meng, Chen Mengni, Wang Xing, it is fine that Liu builds fair Static Spinnings ZnO/ carbon composite nanos
Dimension modified electrode is prepared and to the measure analytical chemistry of trace lead, 2014,42 (7)：985-990), ZnO modified electrodes can be explained
As the importance of sensing material.But zinc oxide poorly conductive, specific surface area needs further to improve, so as to increase sensor
Sensitivity and selectivity.Graphene has good electric conductivity, thus has electricity higher to some specific electricity pair and substrate
Catalytic performance, and with high-specific surface area and biocompatibility, the large biological molecules such as bioprotein or enzyme are had been used at present
Fixation and particular organisms electrochemical sensor making, thus graphene particles are adsorbed on zinc oxide nano fiber and can made
Modified electrode electrochemical response is sensitiveer.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of zinc oxide nano mitron/graphene composite film modified electrode
Preparation method, the obtained product of the present invention is easy to make due to its, and cost is relatively low, good stability, the oxidation of its electrode modified material
Zinc nanotube specific surface area is big, and surface can be coordinated rich in hydroxyl with heavy metal ion, adsorb its surface Graphene more
Its electric conductivity is increased, thus there is sensitive sound in trace heavy metal plumbum ion concentration in determining water body as sensing electrode
Should.
A kind of preparation method of zinc oxide nano mitron/graphene composite film modified electrode of the invention, including：
(1) by high molecular polymer and the dissolving of zinc salt compound in organic solvent, mixed solution is formed, is then heated
To slightly yellow spinning precursor liquid, electrostatic spinning obtains polymer/salt compounds composite nano fiber precursor；
(2) above-mentioned polymer/salt compounds composite nano fiber precursor is aoxidized in air atmosphere, is obtained oxygen
Change zinc nanotube (hollow tubular zinc oxide nano fiber)；
(3) Graphene is dissolved in solvent with zinc oxide nano mitron and is mixed, add Nafion to obtain suspension, then modified
In on electrode, obtaining final product zinc oxide nano mitron/graphene composite film modified electrode；Wherein Graphene, the quality of zinc oxide nano mitron
Concentration ratio is 3:1-1:5.
High molecular polymer is the mixture of polyvinylpyrrolidone and polyacrylonitrile in the step (1), wherein poly- second
The mass ratio of alkene pyrrolidone and polyacrylonitrile is 2：1-3：4.
Zinc salt compound is zinc acetate, zinc chloride, zinc nitrate, zinc sulfate, zinc oxalate, zinc citrate in the step (1)
In one or more；Organic solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, toluene, N- methyl
One or more in pyrrolidones, chloroform, dichloromethane.
The weight/mass percentage composition of high molecular polymer is 15%-20%, zinc salt chemical combination in mixed solution in the step (1)
The weight/mass percentage composition of thing is 15%-20%.
Heating-up temperature is 50-60 DEG C in the step (1), and the time is 3-5h.
Electrostatic spinning process parameter is in the step (1)：Voltage is 9-15kV, and spinning solution flow is 0.5-1.5mL/h,
Needle diameter is 0.8-1.5mm, and syringe needle is 10-20cm with distance between plates is received, and spinning temperature is 15-25 DEG C, and relative humidity exists
30%-37%.Oxidation is specially in the step (2)：With the speed of 20-30 DEG C/h 500-600 DEG C is risen to from room temperature and keep
1-2h。
Solvent is ethanol in the step (3)；The volumn concentration of Nafion is 0.005%-0.01%.
Electrode is the one kind in glass-carbon electrode, gold electrode, silver electrode, conductive glass electrode in the step (3)；Modify in
The method of electrode is drop-coating.
Zinc oxide nano mitron/graphene composite film the modified electrode of gained is applied to underwater trace weight in the step (3)
The detection of metal plumbum ion concentration.
Graphene particles are adsorbed on zinc oxide nano mitron in step (3).
Nafion is perfluor polystyrolsulfon acid solution in the step (3).
The structure of zinc oxide nano mitron-graphene composite film proposed by the invention is：Zinc oxide hollow round tubular nanometer
Uniform attachment activity graphene particle on tunica fibrosa.Electro-chemical test shows that prepared zinc oxide nano mitron-Graphene is combined
Film modified electrode is in 1mmol/L [Fe (CN)6]3-Electrochemical response is stronger in solution, and the test limit for plumbum ion concentration is relatively low.
The compound activity that increased modified electrode adsorption heavy metal ion of the zinc oxide hollow circular tube nanofiber and Graphene
Site.
The zinc oxide nano fiber/graphene composite film thickness can be regulated and controled by changing decorating liquid modification amount；Oxidation
The pipe porosity and internal diameter of zinc hollow round tubular nanofiber can be by changing two kinds of polymerizations in Static Spinning precursor solution
The concentration ratio of thing is effectively controlled.
Beneficial effect
(1) present invention use electrospinning process prepare zinc oxide hollow round tubular nanofiber (zinc oxide nano mitron) for
Main electrode modified material, its specific surface area is greatly improved；
(2) zinc oxide surface is rich in hydroxyl, can be with heavy metal coordination, so as to increase the active adsorption sites of metal ion
The adsorption and enrichment of heavy metal is greatly improved, so as to improve electrode sensitivity；
(3) present invention is conductive agent from Graphene and is effectively attached on zinc oxide nano mitron so that modified electrode is led
Electrically enhancing, with good chemical property；
(4) electrode prepared by the present invention has good stability, and anti-interference is good, can be common in contents of many kinds of heavy metal ion
In the presence of accurate detection trace lead ion concentration.Electrode favorable reproducibility, low manufacture cost can be examined fast and effeciently
Measure concentration of heavy metal ion in water.
Brief description of the drawings
Fig. 1：Through electrostatic spinning polymer/zinc salt compound composite nano fiber precursor (PAN in the embodiment of the present invention 1:
PVP=1:2) SEM figures；
Fig. 2：Zinc oxide hollow circular tube nanofiber (PAN is obtained in the embodiment of the present invention 1:PVP=1:2) SEM figures；Its
Middle illustration is zinc oxide hollow circular tube nanofiber (PAN:PVP=1:2) SEM figures amplify the image after 20 times；
Fig. 3：Through electrostatic spinning polymer/zinc salt compound composite nano fiber precursor (PAN in the embodiment of the present invention 3:
PVP=1:1) SEM figures；
Fig. 4：Zinc oxide hollow circular tube nanofiber (PAN is obtained in the embodiment of the present invention 3:PVP=1:1) SEM figures；Its
Middle illustration is zinc oxide hollow circular tube nanofiber (PAN:PVP=1:1) SEM figures amplify the image after 20 times；
Fig. 5：Zinc oxide nano mitron-graphene composite film modified electrode (b) and sheet in bare electrode (a), the embodiment of the present invention 1
Zinc oxide nano mitron maintenance decorations electrode (c) is in 1mmol/L [Fe (CN) in inventive embodiments 16]3-In cyclic voltammetry scan；
Fig. 6：Containing 2.4 × 10-8mol/L Pb2+HAc-NaAc cushioning liquid in, using oxygen in the embodiment of the present invention 1
Change zinc oxide nano mitron-graphene composite film modified electrode in the complex film modified electrode (a) of zinc nanotube-graphene alkene, example 3
In (b), example 2 zinc oxide nano mitron modified electrode (c) and bare glassy carbon electrode (d) to be scanned the Stripping Voltammetry for obtaining bent
Line；
Fig. 7：The zinc oxide nano mitron of the embodiment of the present invention 1-graphene composite film modified electrode is containing different Pb2+The vinegar of concentration
Stripping Voltammetry curve (A) and linear relationship chart (B) in acid sodium solution；
Fig. 8：Pb in the embodiment of the present invention 12+With the Cd of its isoconcentration2+, Cu2+, Hg+In zinc oxide nano mitron-stone when coexisting
Square wave Stripping Voltammetry figure on the black complex film modified electrode of alkene.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
First, 0.5625g polyacrylonitrile (PAN) is dissolved in 3.25mL N,N-dimethylformamides (DMF) solution,
Then 1.125g polyvinylpyrrolidones (PVP) and 0.3g zinc acetate dihydrates are added thereto to again, finally add 6.5mL DMF
Solution, constant temperature stirring certain hour, forms homogeneous micro- yellow sticky electrospinning precursor liquid in 60 DEG C of water-baths.Adjusting spinning voltage is
10.0kV, it is 10cm to receive distance, and jet velocity is 1mL/h, carries out electrostatic spinning, and collection is received in the flat board for being lined with aluminium foil
On device, Zn (Ac) is obtained2- PAN-PVP composite nano fiber precursor, such as Fig. 1.Be placed on afterwards in Muffle furnace from room temperature with
The speed of 25 DEG C/h rises to 600 DEG C and stops 2h and finally gives ZnO nanotube/, such as Fig. 2, before gained ZnO nanotube/compares calcining
Diameter is obviously reduced, and tube wall is mutually combined into a class hexagon by the arrangement of ZnO nano particle, and surface is formed after being layering
Nanofiber pipe with fine and close pore structure, ZnO nano particle is about 40-60 nanometers, and bore is about 80-100
Nanometer, external diameter is about 160-180 nanometers.The fiber precursor it can also be kept to construct through 650 DEG C of high-temperature calcinations because
A certain amount of PAN is added in the spinning solution of electrostatic spinning so that its fiber reinforcement is remained to when calcining heat is up to about 400 degree
Keep preferable form.
By obtained ZnO nanotube/and Graphene with mass concentration ratio 100 (mg/L):50 (mg/L) are dispersed in absolute ethyl alcohol
In (total mass fraction 0.02%), and with Ultrasound Instrument ultrasound more than about 1 hour, afterwards add 0.005%Nafion continue ultrasound
Concussion 30min is allowed to well mixed.The above-mentioned μ L drop coatings of mixed liquor 5 are drawn in clean glassy carbon electrode surface with microsyringe,
Naturally film forming is dried, zinc oxide nano mitron-graphene composite film modified glassy carbon electrode is obtained.
Embodiment 2 (check experiment)
ZnO hollow Nano fiber in use obtained in embodiment 1 is dispersed in absolute ethyl alcohol (ZnO hollow Nano fiber in use quality is dense
It is 100mg/L to spend), and it is ultrasonic more than about 1 hour with Ultrasound Instrument, 0.005%Nafion is added afterwards continues ultrasonic vibration 30min
It is allowed to well mixed.The above-mentioned μ L drop coatings of mixed liquor 5 are drawn in clean glassy carbon electrode surface with microsyringe, are dried into naturally
Film, obtains zinc oxide nano mitron modified glassy carbon electrode.
Embodiment 3
First, 0.5625g polyacrylonitrile (PAN) is dissolved in 3.25mL N,N-dimethylformamides (DMF) solution,
Then 0.5625g polyvinylpyrrolidones (PVP) and 0.3g zinc chloride are added thereto to again, finally add 6.5mL DMF molten
Liquid, constant temperature stirring certain hour, forms homogeneous micro- yellow sticky electrospinning precursor liquid in 60 DEG C of water-baths.Adjusting spinning voltage is
10.0kV, it is 10cm to receive distance, and jet velocity is 1mL/h, carries out electrostatic spinning, and collection is received in the flat board for being lined with aluminium foil
On device, Zn (Ac) is obtained2- PAN-PVP composite nano fiber precursor (PAN/PVP=1:1), such as Fig. 3.Horse is placed on afterwards
Not rise to 600 DEG C and stop 2h with the speed of 25 DEG C/h from room temperature in stove and finally give ZnO nanotube/, such as Fig. 4.By Fig. 1 and Fig. 3
Compare discovery, by polyvinylpyrrolidone (PVP) Mass lost added in electrospinning precursor liquid in embodiment 3 so that Fig. 3
In fiber precursor diameter (200nm or so) it is relatively thin compared with the fiber precursor diameter (400nm or so) in Fig. 1, and roughness is obvious
Increase, and grain shape projection phenomenon is presented, Fiber Uniformity is deteriorated.After peroxidating, the nano particle of ZnO nanotube/in Fig. 4
About 20-30nm, ZnO nanotube/internal diameter is only 10-30nm, and external diameter is about 160-200nm, compares Fig. 2, and its is intergranular
Degree of adhesion increases, and hollow space space is reduced in its nanotube, illustrates that prepared ZnO nanotube/in embodiment 3 is adsorbable heavy
The avtive spot of metal ion does not have prepared ZnO nanotube/in embodiment 1 many.
By obtained ZnO nanotube/and Graphene with mass concentration ratio 100 (mg/L):50 (mg/L) are dispersed in absolute ethyl alcohol
In (total mass fraction 0.02%), and with Ultrasound Instrument ultrasound more than about 1 hour, afterwards add 0.005%Nafion continue ultrasound
Concussion 30min is allowed to well mixed.The above-mentioned μ L drop coatings of mixed liquor 5 are drawn in clean glassy carbon electrode surface with microsyringe,
Naturally film forming is dried, zinc oxide nano mitron-graphene composite film modified glassy carbon electrode is obtained.
Embodiment 4
By zinc oxide nano mitron-graphene composite film modified electrode, example two prepared in bare glassy carbon electrode, example one
In prepared zinc oxide nano mitron modified electrode be respectively placed in 1mmol/L [Fe (CN)6]3-In, in 0-0.5V potential ranges
Voltammetric scan is circulated, cyclic voltammetry curve, such as Fig. 5 is obtained.Corresponding redox peaks completely reversibility in bare glassy carbon electrode,
The nearly 70mV of peak-to-peak differential.On zinc oxide nano fiber modified electrode surface, peak current has obvious suppression, peak-to-peak difference increase, table
Now be defined invertibity.Mainly due to pure ZnO nano fiber, electric conductivity is relatively low in itself for this, electron transmission is obstructed.And nanotube-
On graphene composite film modified electrode, [Fe (CN)6]3-Response significantly improved compared to zinc oxide electrode, on the one hand explanation oxidation
The electric conductivity of zinc nano composite membrane decorative layer is good, promotes electro transfer.
Embodiment 5
According to modified electrode and bare glassy carbon electrode obtained by example one, two, three, to Pb2+Standard liquid is measured, and takes
HAc-NaAc (0.1mol/L) cushioning liquid of 10.0mL pH=4.6, adds a certain amount of Pb2+Standard liquid.It is molten using square wave
Go out voltammetry (SWV), in enrichment 10min, static 10s is stirred under -1.0V current potentials, record Pb in -0.8V-0.1V potential ranges2+
Stripping Voltammetry figure, such as Fig. 6.Modified electrode wherein obtained in example one is the strongest for the response of trace plumbum ion concentration
It is strong.Independent linear test is carried out for modified electrode detection trace lead ion.Such as Fig. 7, it is clear that with Pb in solution2+'s
Concentration increases, and its dissolution peak current gradually strengthens.The dissolution peak current of lead is with its concentration 2.4 × 10-9-4.8×10-7mol/L
Good linear relation is presented in concentration range.Thus corresponding equation of linear regression is:Ip (μ A)=0.469c-1.544 is related
Coefficient r=0.9970, the minimal detectable concentration of electrode is 4.8 × 10-10mol/L。
Embodiment 6
Same concentrations 4 have been investigated with reference to zinc oxide nano mitron-graphene composite film modified electrode obtained in example one
Heavy metal species ion (Cd2+, Pb2+, Cu2+, Hg2+) detection case when coexisting.Such as Fig. 8,4 kinds of ions are in respective dissolution current potential
There is obvious dissolution peak in place, and each with the increase (2.4 × 10 of concentration-7mol/L、3.36×10-7mol/L、4.8×10-7Mol/L), its dissolution peak current gradually strengthens.Thus the avtive spot of the modified electrode adsorption heavy metal ion can be explained
It is more, and the absorption of other heavy metal ion is not significantly affected by Pb2+Measure.
Claims (10)
1. a kind of preparation method of zinc oxide nano mitron/graphene composite film modified electrode, including：
(1) by high molecular polymer and the dissolving of zinc salt compound in organic solvent, mixed solution is formed, then heating is spun
Silk precursor liquid, electrostatic spinning obtains polymer/salt compounds composite nano fiber precursor；
(2) above-mentioned polymer/salt compounds composite nano fiber precursor is aoxidized in air atmosphere, is obtained zinc oxide
Nanotube；
(3) Graphene is dissolved in solvent with zinc oxide nano mitron and is mixed, add Nafion to obtain suspension, then modified in electricity
Extremely go up, obtain final product zinc oxide nano mitron/graphene composite film modified electrode；Wherein Graphene, the mass concentration of zinc oxide nano mitron
Ratio is 3:1-1:5.
2. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：High molecular polymer is the mixture of polyvinylpyrrolidone and polyacrylonitrile, wherein polyethylene in the step (1)
The mass ratio of pyrrolidones and polyacrylonitrile is 2：1-3：4.
3. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Zinc salt compound is in zinc acetate, zinc chloride, zinc nitrate, zinc sulfate, zinc oxalate, zinc citrate in the step (1)
One or more；Organic solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, toluene, N- methyl pyrroles
One or more in pyrrolidone, chloroform, dichloromethane.
4. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：The weight/mass percentage composition of high molecular polymer is 15%-20%, zinc salt chemical combination in mixed solution in the step (1)
The weight/mass percentage composition of thing is 15%-20%.
5. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Heating-up temperature is 50-60 DEG C in the step (1), and the time is 3-5h.
6. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Electrostatic spinning process parameter is in the step (1)：Voltage is 9-15kV, and spinning solution flow is 0.5-1.5mL/h,
Needle diameter is 0.8-1.5mm, and syringe needle is 10-20cm with distance between plates is received, and spinning temperature is 15-25 DEG C, and relative humidity exists
30%-37%.
7. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Oxidation is specially in the step (2)：With the speed of 20-30 DEG C/h 500-600 DEG C is risen to from room temperature and keep 1-
2h。
8. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Solvent is ethanol in the step (3)；The volumn concentration of Nafion is 0.005%-0.01%.
9. the preparation method of a kind of zinc oxide nano mitron/graphene composite film modified electrode according to claim 1, it is special
Levy and be：Electrode is the one kind in glass-carbon electrode, gold electrode, silver electrode, conductive glass electrode in the step (3)；Modification electricity
The method of pole is drop-coating.
10. a kind of application of zinc oxide nano mitron/graphene composite film modified electrode, it is characterised in that：To be walked in claim 1
Suddenly the zinc oxide nano mitron/graphene composite film modified electrode obtained by (3) is applied to underwater trace heavy metal lead ion concentration
Detection.
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| CN107727719B (en) * | 2017-10-17 | 2019-07-23 | 浙江大学 | A kind of preparation method of composite oxide of metal doped graphene film modified electrode |
| CN108598428A (en) * | 2018-04-26 | 2018-09-28 | 东华大学 | A kind of graphene/stannic oxide alternating layers stack composite fibre and its preparation method and application |
| CN109273605A (en) * | 2018-10-01 | 2019-01-25 | 河北工程大学 | A kind of graphene solar battery and preparation method thereof |
| CN109485088A (en) * | 2019-01-09 | 2019-03-19 | 安徽工程大学 | A kind of flower shape zinc oxide nanometer sheet aggregate material and preparation method thereof, application |
| CN110055680A (en) * | 2019-05-10 | 2019-07-26 | 上海纳旭实业有限公司 | The preparation method and product of nano cellulose composite film and application |
| CN111272839A (en) * | 2020-02-15 | 2020-06-12 | 青岛科技大学 | Preparation, application and method of electrochemical sensor based on nano composite material |
| CN117867761B (en) * | 2024-01-04 | 2024-10-15 | 中南大学 | Preparation method and application of semiconductor sulfide composite nanofiber membrane |
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