CN103439388B - Method for preparing functionalized composite nano-fiber modified electrode - Google Patents
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Abstract
The invention relates to method for preparing a functionalized composite nano-fiber modified electrode. The method specifically comprises the steps of (1) preparing a spinning solution; (2) preparing composite nano-fibers through electrostatic spinning so as to form a composite nano-fiber PA6-MWNTs modified electrode; (3) carrying out electrical-polymerization thionine functionalization on the composite nano fibers: soaking the composite nano-fiber PA6-MWNTs modified electrode into a polymerization solution containing thionine monomers PTH, applying a voltage to the modified electrode so as to carry out anodizing treatment, then, carrying out cyclic volt-ampere scanning, washing away the thionine monomers, adsorbed to the modified electrode, by using a phosphate buffer solution PBS, forming a functionalized composite nano-fiber electrode modification material PA6-MWNTs/PTH layer on the surface of the electrode after the polymerization reaction is ended, thus obtaining the functionalized composite nano-fiber PA6-MWNTs/PTH modified electrode. According to the method, a functionalized composite nano-fiber electrode modification material which has the characteristics of good stability, large specific surface area, good biocompatibility, high electron transfer rate, uniformly-distributed diameter and pore size, and the like is obtained.
Description
Technical field
The invention discloses a kind of preparation method of functionalization composite nano fiber modified electrode.Belong to nanometer material modified electrode field.
Background technology
Electrostatic spinning modified electrode is the method for a kind of modified electrode just risen in the last few years, has developing potentiality.So far, electrostatic spinning modified electrode roughly can be divided into two large classes according to the difference of method of modifying: the direct modified electrode of electrostatic spinning and non-immediate modified electrode.The direct modified electrode of electrostatic spinning refers to, replaces traditional fiber accepts screen with bare electrode, directly by electrospinning fiber collecting out at electrode surface.Obtain fiber-modified electrode by this method of modifying and can be applicable to galvanochemistry and biology sensor.Electrostatic spinning non-immediate modified electrode refers to, first prepares micro/nano-fibre by electrostatic spinning and aftertreatment (such as high-temperature heat treatment etc.) technology, then by being fixed at the electrode surface by the fiber prepared with fixing agent (as Nafion).Compared with electrostatic spinning non-immediate modified electrode, electrode is utilized to shield as fiber accepts, by electrostatic spinning technique directly by fiber-modified at electrode surface, not only operating process is simple and convenient for this modification mode, the more important thing is and fiber can be made directly to contact with electrode, be conducive to electronics and transmit rapidly and directly between fiber and electrode.
At present, material with carbon element is applied
[1-3], metal oxide
[4], macromolecular material
[5]etc. single
[6], compound
[7,8]the bibliographical information that nanofiber modifies various electrode is more, and ubiquity nanofiber electric conductivity, stability and poor biocompatibility and modified electrode specific surface area amplify the problems such as remarkable not.If the nano material (functionalized multi-wall carbonnanotubes) of good conductivity adulterated with the spun macromolecule (nylon 6) of good stability obtain presoma electrostatic spinning solution, obtain conduction composite nano fiber modified electrode through electrostatic spinning; Modify (electropolymerization thionine monomer) through electricity again on conduction composite nano fiber, to wrap up the conduction of one deck porous 3D structure, carry the conducting polymer superpolymer of a large amount of reactive group, the method obtaining functionalization composite nano fiber electrode modified material thus has no pertinent literature report both at home and abroad.Described functionalization composite nano fiber electrode modified material amplifies through the superposition of twice advantage, can overcome the defect of Existing methods, make it have conduct electricity very well, good stability, effective ratio area are large and biocompatibility is good characteristic.Functionalization composite nano fiber modified electrode is conducive to being used widely in bio-sensing context of detection.
List of references:
[1]Jianshe Huang,Yang Liu,Tianyan You,Carbon nanofiber basedelectrochemical biosensors:Areview.Analytical Methods,2010,2,202-211.
[2]QiaohuiGuo,Jianshe Huang,Tianyan You,Electrospunpalladiumnanoparticle-loaded carbon nanofiber for methanol electro-oxidation.Chinese Journal of Analytical Chemistry,2013,41,210-214.
[3]Tapas Kuila,Saswata Bose,ParthaKhanra,Ananta Kumar Mishra,NamHoonKim,JoongHee Lee,Recent advances in graphene-based biosensors.Biosensors and Bioelectronics,2011,26,4637-4648.
[4]Shan Huang,Yu Ding,Yixin Liu,Liang Su,Raymond Filosa Jr.,YuLei,Glucose biosensor using glucose oxidase and electrospunMn
2O
3-Agnanofibers.Electroanalysis,2011,23(8),1912-1920
[5]ZhengangWang,LingshuWan,Zhenmei Liu,Xiaojun Huang,ZhikangXu,Enzyme immobilization on electrospun polymer nanofibers:Anoverview.Journal of Molecular Catalysis B:Enzymatic,2009,56,189-195.
[6]Lei Qiu,Ziqiang Shao,Mingshan Yang,Wenjun Wang,Feijun Wang,LongXie,ShaoyiLv,Yunhua Zhang,Electrospuncarboxymethyl celluloseacetate butyrate(CMCAB)nanofiber for high rate lithium-ion battery.Carbohydrate Polymers,2013,96,240-245.
[7]Jun Zhang,YajunDuan,DiWei,Lianyong Wang,HongjunWang,ZhongweiGu,Deling Kong,Co-electrospun fibrous scaffold-adsorbed DNAforsubstrate-mediated gene delivery.Journal of Biomedical MaterialsResearch A,2011,96,212-220
[8]ZhaofeiOuyang,JingfengLi,Jinhui Wang,QianLi,Tongyang Ni,XiaoyuanZhang,Haixia Wang,Qing Li,Zhiqiang Su,Gang Wei,Fabrication,characterization and sensor application of electrospun polyurethanenanofibers filled with carbon nanotubes and silver nanoparticles.Journal of Materials Chemistry B,2013,1,2415-2424.
Summary of the invention
Technical matters: the preparation method that the object of this invention is to provide a kind of functionalization composite nano fiber modified electrode, the present invention modifies in conjunction with electrostatic spinning technique, electricity, obtains the functionalization composite nano fiber electrode modified material with features such as good stability, specific surface area are large, biocompatibility is good, electron transport rate is fast, diameter apertures is evenly distributed.Functionalization composite nano fiber modified electrode is conducive to being used widely in bio-sensing context of detection.
Technical scheme: the preparation method of a kind of functionalization composite nano fiber modified electrode provided by the invention is: (1) by a certain amount of nylon 6, functionalized multi-wall carbonnanotubes in a suitable solvent room temperature stir continuously, the presoma electrostatic spinning solution of obtained homogeneous transparent, utilize electrostatic spinning technique, it is deposited on clean bare electrode with the nonwoven fabrics form of lack of alignment, obtains composite nano fiber modified electrode; (2) electrode that (1) obtains first is carried out anodization in the damping fluid containing thionine monomer, then cyclic voltammetry scan is carried out, be polymerized the thionine film of one deck densification in the surface electrical of composite nano fiber, obtain functionalization composite nano fiber electrode modified material.Described functionalization composite nano fiber electrode modified material technique is simple, easy to operate, raw material sources are extensive, cost is low, and productive rate is high; Have the features such as good stability, specific surface area is large, biocompatibility is good, electron transport rate is fast, diameter apertures is evenly distributed, functionalization composite nano fiber modified electrode is conducive to being used widely in bio-sensing context of detection.
Relevant writing a Chinese character in simplified form is described as follows:
Nylon 6(PA6)
Functionalized multi-wall carbonnanotubes (MWNTs)
Thionine monomer (PTH)
Composite nano fiber (PA6-MWNTs)
Function and service nanofiber electrode decorative material (PA6-MWNTs/PTH)
Naked glass-carbon electrode (GC)
Composite nano fiber modified electrode (PA6-MWNTs/GC)
Function and service nanofiber modified electrode (PA6-MWNTs-PTH/GC)
Poly-thionine modified electrode (PTH/GC)
Field emission scanning electron microscope (FESEM)
Differential pulse voltammetry figure (DPV)
Method of the present invention is specific as follows:
1) spinning solution preparation:
Nylon 6 is dissolved in 1:1 ~ 19:1 with functionalized multi-wall carbonnanotubes MWNTs, forms PA6-MWNTs potpourri in the mixed solvent of the metacresol/formic acid of v/v, then this potpourri is at room temperature stirred continuously, the presoma electrostatic spinning solution of obtained homogeneous transparent;
2) electrostatic spinning prepares composite nano fiber:
When electrostatic spinning, the presoma electrostatic spinning solution of the homogeneous transparent of above-mentioned preparation is placed in syringe, the positive pole of HV generator connects syringe needle, negative pole is connected on clean bare electrode, adopt micro-injection pump feed flow, the high-pressure electrostatic produced by HV generator is applied directly on syringe needle, and composite nano fiber PA6-MWNTs is collected on bare electrode, forms composite nano fiber PA6-MWNTs modified electrode;
3) composite nano fiber electropolymerization thionine functionalization:
Composite nano fiber PA6-MWNTs modified electrode is dipped in the polymer fluid containing thionine monomer PTH, first voltage is applied to this modified electrode and carry out anodization, then cyclic voltammetry scan is carried out, last modified electrode phosphate buffer solution PBS washes away the thionine monomer be adsorbed on modified electrode, after polyreaction terminates, electrode face finish last layer functionalization composite nano fiber electrode modified material PA6-MWNTs/PTH.Thus, functionalization composite nano fiber PA6-MWNTs/PTH modified electrode is obtained.
Beneficial effect:
(1) modified electrode specific surface area is large
Composite nano fiber (PA6-MWNTs) random orientation on bare electrode forms the nano fibrous membrane (see accompanying drawing 1,2) of porous 3D structure.Compare with bare electrode, the specific surface area amplification (see accompanying drawing 5) more remarkable in bare electrode of composite nano fiber modified electrode.Composite nano fiber modified electrode, again through electropolymerization thionine (PTH) functionalization, generates the fine and close decorative layer (see accompanying drawing 3,4) with porous structure, has larger specific surface area.The specific surface area of the comparatively poly-thionine modified electrode (PTH/GC) of specific surface area of function and service nanofiber modified electrode (MWNTs-PA6-PTH/GC), naked glass-carbon electrode is amplified 3.2,10.3 times (seeing attached list 1) respectively.
(2) biocompatibility is good
There is the self-contained amino positively charged in a large number of fine and close thionine decorative layer of porous structure, both with electronegative DNA phosphate backbones, the direct electrostatic attractions of bioactive molecule probe such as the albumen of cysteamine residue, enzyme can be had; Also can pass through the bioactive molecule probe of covalently immobolization phosphate, hydroxyl or carboxyl isoreactivity base group modification, there is good biocompatibility.
(3) electron transport rate is fast
Functionalized multi-wall carbonnanotubes (MWNTs) is entrained in nylon 6(PA6) in, the electron transmission ability that the large specific surface area remaining MWNTs is become reconciled.Thionine is a kind of dyestuff with redox active, heterocycle structure has two to the amino of electronic property, can and another monomer molecule ortho position or a position on carbon atom there is coupling reaction from beginning to end, so thionine forms the polymkeric substance with redox active by Raolical polymerizable.The double action of functionalized multi-wall carbonnanotubes (MWNTs) and thionine, makes functionalization composite nano fiber electrode modified material (PA6-MWNTs-PTH) electron transport rate fast, has good electric conductivity.
(4) modified electrode good stability
Containing amide group and methylene in the molecular backbone segment unit of nylon 6 (PA6); because C-N has the character of partial double bond; make amide group in the same plane; the arrangement that whole backbone molecule is orderly, the methylene segment between amino and acyl group obtains maximum hydrophobicity.Be that functionalization composite nano fiber modified electrode prepared by template macromolecule has good electrochemical response and stability in neutral buffered liquid with PA6, preserve after 2 days in phosphate buffer, current-responsive is almost constant.
Accompanying drawing explanation
Fig. 1 is the FESEM image of PA6-MWNTs.
Fig. 2 is the enlarged drawing of Fig. 1.
Fig. 3 is the FESEM image of PA6-MWNTs/PTH.
Fig. 4 is the enlarged drawing of Fig. 3.
Fig. 5 is PTH/GC(a) and differential pulse voltammetry figure PA6-MWNTs-PTH/GC(b).A figure is oxidizing process, and B figure is reduction process.Sweep limit is+0.2 to-0.4V, and amplitude is 0.05V, pulse width 0.05s, recurrence interval 0.5s.
Embodiment
Micromorphologic sign has been carried out respectively to PA6-MWNTs and PA6-MWNTs-PTH.Can be found out by the field emission scanning electron microscope collection of illustrative plates (FESEM) (Fig. 1, Fig. 2) of PA6-MWNTs, PA6-MWNTs random orientation forms the nano fibrous membrane of porous 3D structure, and nanofiber surface is smooth, and without lofty, diameter range is from 50nm to 300nm.When after the polymerization thionine PTH that powers at PA6-MWNTs nanofiber (Fig. 3, Fig. 4), nanofiber diameter is obviously thicker, and diameter range is from 100nm to 500nm.Find out from amplification collection of illustrative plates, nanofiber surface is no longer smooth, and surface is obviously seen and wrapped up in a skim.Contrasted by the microscopic appearance of the nanofiber before and after electropolymerization thionine and can draw nanofiber surface success electropolymerization one deck thionine.
Respectively with naked glass-carbon electrode (GC) and composite nano fiber modified electrode (PA6-MWNTs/GC) electropolymerization thionine (PTH) under identical condition.After electropolymerization thionine, PA6-MWNTs-PTH/GC electrode and PTH/GC electrode carry out differential pulse voltammetry scanning (DPV) (Fig. 5) under similarity condition, the oxidation peak (Fig. 5 A) of the former thionine and all obvious than the latter increase of reduction peak (Fig. 5 B).Therefore can draw, compare with bare electrode, the amount of the thionine that PA6-MWNTs/GC electrode is polymerized obviously increases, i.e. the specific surface area of composite nano fiber modified electrode amplification more remarkable in bare electrode.
According to Randles-Sevcik equation, i
p=2.69 × 10
5n
3/2aD
1/2v
1/2c, wherein, i
pfor the electric current of modified electrode in electroactive material, receiving and losing electrons number when n is electroactive material oxidation, A is electrode area, and D is coefficient of diffusion (298K, D=0.76 × 10
-5cm
2/ s), v is sweep speed, and C is the concentration of electroactive material.Under difference sweeps speed (0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.1V/s), successively measure PTH/GC electrode, MWNTs-PA6-PTH/GC electrode respectively 5.0 × 10
-3peak current i in mol/L potassium ferricyanide solution (containing 1.0mol/LKCl)
p, use i
pto v
1/2to linearly, slope is the true specific surface area of modified electrode.The true specific surface area of MWNTs-PA6-PTH/GC electrode amplifies 3.2,10.3 times respectively compared with the specific surface area of PTH/GC electrode, naked glass-carbon electrode, and concrete numerical value is in table 1.
The parameter of the various modified electrode of table 1 compares.
*
* GC electrode (diameter 3mm).
Concrete steps of the present invention are:
(1) spinning solution preparation:
By the nylon 6(PA6 of 3.2g, viscosity is 2.2) be dissolved in (metacresol: formic acid=6:4 in the mixed solvent of 10mL with 5mg functionalized multi-wall carbonnanotubes (MWNTs), v/v), potpourri is at room temperature stirred 12 hours continuously, the presoma electrostatic spinning solution of obtained homogeneous transparent.
(2) electrostatic spinning prepares composite nano fiber:
When electrostatic spinning, the presoma electrostatic spinning solution of the homogeneous transparent of above-mentioned preparation is placed in syringe, the positive pole of HV generator connects syringe needle, negative pole is connected on clean bare electrode, adopt micro-injection pump feed flow, the high-pressure electrostatic produced by HV generator is applied directly on syringe needle, and composite nano fiber (PA6-MWNTs) is collected on bare electrode;
Electrospinning conditions is arranged: 6
1/
2~ 9
1/
2number syringe needle, voltage: 17 ~ 23V, syringe flow velocity: 0.1 ~ 0.8mL/h, syringe needle and electrode distance 15 ~ 20cm, the spinning time is 3 ~ 5min, and environment temperature is 20 ~ 25 DEG C, and humid control is 30 ~ 40%;
(3) composite nano fiber electropolymerization thionine functionalization:
Composite nano fiber (PA6-MWNTs) modified electrode is dipped in 5mL and contains 1.0 × 10
-4in the polymer fluid (end liquid is 0.1mol/LPBS, pH6.0) of mol/L thionine monomer (PTH), apply+1.5V voltage 10min and anodization is carried out to this modified electrode, then cyclic voltammetry scan is carried out, scanning current potential :-0.40 ~+0.15V, sweeps speed: 50mV/s, the scanning number of turns: 15 circles.Last modified electrode 0.1mol/LPBS (pH6.0) solution washes away the thionine monomer be adsorbed on modified electrode.The hepatic film of electrode face finish last layer can be seen after polyreaction terminates.Obtain functionalization composite nano fiber electrode modified material (PA6-MWNTs/PTH).Thus, functionalization composite nano fiber PA6-MWNTs/PTH modified electrode is obtained.
The present invention for naked glass-carbon electrode, other electrode as gold electrode, graphite electrode, platinum disk electrode etc. all can carry out as described in material modification.
Claims (1)
1. a preparation method for functionalization composite nano fiber modified electrode, is characterized in that described preparation method is:
1) spinning solution preparation:
Nylon 6 is dissolved in 1:1 ~ 19:1 with functionalized multi-wall carbonnanotubes MWNTs, forms PA6-MWNTs potpourri in the mixed solvent of the metacresol/formic acid of v/v, then this potpourri is at room temperature stirred continuously, the presoma electrostatic spinning solution of obtained homogeneous transparent;
2) electrostatic spinning prepares composite nano fiber:
When electrostatic spinning, the presoma electrostatic spinning solution of the homogeneous transparent of above-mentioned preparation is placed in syringe, the positive pole of HV generator connects syringe needle, negative pole is connected on clean bare electrode, adopt micro-injection pump feed flow, the high-pressure electrostatic produced by HV generator is applied directly on syringe needle, and composite nano fiber PA6-MWNTs is collected on bare electrode, forms composite nano fiber PA6-MWNTs modified electrode;
3) composite nano fiber electropolymerization thionine functionalization:
Composite nano fiber PA6-MWNTs modified electrode is dipped in 5mL containing 1.0 × 10
-4the polymer fluid of mol/L thionine monomer PTH, its end liquid of described polymer fluid is 0.1mol/L PBS, and pH value is 6.0; Apply+1.5V voltage 10min and carry out anodization to this modified electrode, then carry out cyclic voltammetry scan, scanning current potential :-0.40 ~+0.15V, sweeps speed: 50mV/s, the scanning number of turns: 15 circles; Last modified electrode phosphate buffer solution PBS washes away the thionine monomer be adsorbed on modified electrode, after polyreaction terminates, and electrode face finish last layer functionalization composite nano fiber electrode modified material PA6-MWNTs/PTH; Thus, functionalization composite nano fiber PA6-MWNTs/PTH modified electrode is obtained.
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| CN104090011B (en) * | 2014-07-09 | 2017-04-05 | 东南大学 | The preparation method of nanometer gold nanofiber function and service thing modified electrode |
| CN104122255B (en) * | 2014-07-15 | 2016-10-19 | 东南大学 | The ElectrochemiluminescBased Based detection method of aniline |
| CN104483489A (en) * | 2014-12-03 | 2015-04-01 | 东南大学 | Electronic mediator type enzymatic electrochemical immunodetection method of p53 protein |
| CN105004775B (en) * | 2015-07-08 | 2016-02-03 | 青岛大学 | Curing object point/nanometer sheet compound DNA electrochemical probe and its preparation method and application |
| CN106596667B (en) * | 2016-11-24 | 2019-05-03 | 东华大学 | A kind of porous zirconia/carbon nano-composite fiber modified electrode and its preparation and application |
| CN107271513B (en) * | 2017-06-02 | 2019-07-30 | 东南大学 | A kind of silica/nanofiber function and service object modified electrode and its preparation method and application |
| CN108931569B (en) * | 2018-06-28 | 2020-06-26 | 海南师范大学 | Electrochemical analysis application of hemoglobin and titanic acid nanofiber modified carbon ionic liquid electrode |
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