CN104034790A - Perfluorinated sulfonic acid resin modified SnO2-coated ZnO nanotube array electrode used for detecting dopamine and application of nanotube array electrode - Google Patents
Perfluorinated sulfonic acid resin modified SnO2-coated ZnO nanotube array electrode used for detecting dopamine and application of nanotube array electrode Download PDFInfo
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229960003638 dopamine Drugs 0.000 title claims abstract description 43
- 239000002071 nanotube Substances 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical class O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title abstract 3
- 150000003460 sulfonic acids Chemical class 0.000 title abstract 2
- 239000013078 crystal Substances 0.000 claims abstract description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 19
- 238000001903 differential pulse voltammetry Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 13
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000004044 response Effects 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 abstract description 25
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 7
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- 239000000463 material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000725303 Human immunodeficiency virus Species 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 229940088597 hormone Drugs 0.000 description 1
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- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000036403 neuro physiology Effects 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention belongs to the technical field of nano material application, and particularly relates to a perfluorinated sulfonic acid resin (Nafion) modified SnO2-coated ZnO nanotube array electrode used for detecting dopamine and the application of the nanotube array electrode. The nanotube array electrode comprises a conductive substrate and a Nafion modified polycrystal SiO2 nano-particle film-coated single-crystal ZnO nanotube array which vertically grows on the conductive substrate. The Nafion modified SnO2-coated ZnO nanotube array electrode used for detecting the dopamine can be used for detecting the dopamine in water solution; when the nanotube array electrode is taken as a working electrode, a platinum gauze electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a cyclic voltammetry (CV) or differential pulse voltammetry (DPV) is used for detecting the dopamine in water solution, the nanotube array electrode is capable of generating very strong electrochemical signals.
Description
Technical field
The invention belongs to technical field of nano material application, relate in particular to a kind of perfluorinated sulfonic resin for detection of dopamine (Nafion) and modify SnO
2the nanometer pipe array electrode of clading ZnO and application.
Background technology
Dopamine (DA) is a kind of important neurotransmitter, and central nervous system, Hormone system, the cardiovascular system renal function of unifying is played an important role.In human body, the concentration of DA can be followed some major diseases and change, as schizophrenia, Parkinson's disease, senile dementia, HIV (human immunodeficiency virus) infection etc.Therefore, in human body, the detection of DA concentration has great significance for the control of neuro-physiology research, medical diagnosis on disease and related drugs.
Electrochemical sensor is a kind of important means that dopamine detects.In electrochemical sensor, most important element is to produce to dopamine the electrode of response.Because the dopamine concentration in biosome is extremely low, in dopamine testing process, can be subject to coming from the strong interference of ascorbic acid simultaneously, therefore need development to there is the dopamine electrochemical sensor electrodes of high sensitivity and high selectivity.The lifting that develops into dopamine performance of electrochemical sensors of nanosecond science and technology provides good opportunity.Due to its huge specific surface area and special physical/chemical, nano material has been used to constructing of dopamine electrochemical sensor electrodes.Wherein, monodimension nanometer material is as particularly noticeable in nanometer rods, nano wire, nanobelt, nanotube etc.This be because these monodimension nanometer materials except having huge specific surface area, its special one-dimentional structure can also be served as " express passway " of electric charge transmission, and the electronics that participates in electrochemical reaction is transported to external circuit fast, thereby improves the performance of sensor.At present, as most typical monodimension nanometer material, carbon nano-tube is by a large number for dopamine electrochemical sensor electrodes.But at these electrodes, carbon nano-tube is normally distributed in electrode surface in a jumble disorderly, and its effect as charge transport " express passway " fails to be not fully exerted.
Summary of the invention
The object of the invention is in order to overcome the deficiencies in the prior art, provide a kind of for detection of dopamine based on perfluorinated sulfonic resin (Nafion) modify SnO
2the dopamine electrochemical sensor electrodes of the nano-tube array of clading ZnO.
An also object of the present invention is to provide modifies SnO for detection of dopamine based on perfluorinated sulfonic resin (Nafion)
2the application of the dopamine electrochemical sensor electrodes of the nano-tube array of clading ZnO.
Perfluorinated sulfonic resin for detection of dopamine of the present invention (Nafion) is modified SnO
2clading ZnO (SnO
2@ZnO) nanometer pipe array electrode, be by conductive substrates and be vertically grown in the polycrystalline SnO that perfluorinated sulfonic resin (Nafion) in this conductive substrates is modified
2the array of the coated single crystal ZnO nanotube of nano-particular film forms.
Described conductive substrates can be ito glass or FTO glass.
Described polycrystalline SnO
2nano-particular film is coated single crystal ZnO nanotube, is by polycrystalline SnO
2the film that nano particle forms is evenly coated on the inner and outer wall of single crystal ZnO nanotube.
It is by by polycrystalline SnO that described perfluorinated sulfonic resin (Nafion) is modified
2in the Nafion solution that the array of the coated single crystal ZnO nanotube of nano-particular film is 5% in mass concentration, soaking (the general time of soaking is 8～15 minutes) realizes.
Perfluorinated sulfonic resin for detection of dopamine of the present invention (Nafion) is modified SnO
2clading ZnO (SnO
2@ZnO) the preparation method of nanometer pipe array electrode be: first,, prepared ZnO nano-rod array is carried out in inorganic alkaline aqueous solution to etching and obtain single crystal ZnO nano-tube array at the upper making ZnO nanometer stick array of conductive substrates (ito glass or FTO glass) with electrochemical deposition method; Then, having the conductive substrates of single crystal ZnO nano-tube array to grow is substrate, utilizes thermal evaporation to prepare one deck polycrystalline SnO at the surfaces externally and internally of single crystal ZnO nanotube
2nano-particular film; By polycrystalline SnO
2in the Nafion solution that the array of the coated single crystal ZnO nanotube of nano-particular film is 5% in mass concentration, soak (the general time of soaking is 8～15 minutes).
Perfluorinated sulfonic resin for detection of dopamine of the present invention (Nafion) is modified SnO
2clading ZnO (SnO
2@ZnO) nanometer pipe array electrode can detect the dopamine in aqueous solution, using nanometer pipe array electrode of the present invention as working electrode, using platinum plate electrode as to electrode, using saturated calomel electrode as contrast electrode, when the dopamine in aqueous solution detection with cyclic voltammetry (CV) or differential pulse voltammetry (DPV), nanometer pipe array electrode of the present invention can produce extremely strong electrochemical signals.
Described use cyclic voltammetry (CV) or differential pulse voltammetry (DPV) detect the dopamine in aqueous solution, the linear response range of cyclic voltammetry (CV) is 0.1～500 μ M, and the linear response range of differential pulse voltammetry (DPV) is 0.1～2 μ M.
The concentration of the dopamine in described aqueous solution is that 0.1 μ M is to 500 μ M.
In dopamine electrochemical sensor electrodes of the present invention, the SnO that Nafion modifies
2clading ZnO (SnO
2@ZnO) nanotube be to be vertically grown in conductive substrates, to form oldered array, the electronics that electrochemical reaction occurs can be transported to external circuit fast along the nanotube described in person, give full play to the potential of monodimension nanometer material as electric charge transmission " express delivery passage ", effectively improved the performance of dopamine electrochemical sensor.
Brief description of the drawings
Fig. 1. the polycrystalline SnO that the Nafion of the embodiment of the present invention 1 modifies
2the SEM image of the array of the coated single crystal ZnO nanotube of nano-particular film.
Fig. 2. single polycrystalline SnO prepared by the embodiment of the present invention 1
2hRTEM (a) and SAED (b) image of the coated single crystal ZnO nanotube of nano-particular film.
Fig. 3. the CV (a) of the embodiment of the present invention 2 and DPV (b) figure.
Fig. 4. the CV (a) of the embodiment of the present invention 3 and DPV (b) figure.
Fig. 5. the CV (a) of the embodiment of the present invention 4 and DPV (b) figure.
Fig. 6. the CV (a) of the embodiment of the present invention 5 and DPV (b) figure.
Fig. 7. the CV (a) of the embodiment of the present invention 6 and DPV (b) figure.
Fig. 8. the CV figure (a) of the embodiment of the present invention 7 and CV calibration curve (b) and DPV figure (c) and DPV calibration curve (d).
Embodiment
Embodiment 1.
In three-electrode system, using platinized platinum and saturated calomel electrode respectively as to electrode and contrast electrode, taking ito glass or FTO glass as working electrode.Electrolytic solution is the aqueous solution that contains 5mM zinc nitrate and 5mM ammonium acetate.By water-bath, electrolyte temperature is risen to 85 DEG C and maintain 85 DEG C.Utilize the current potential of electrochemical workstation (CHI660C, Shanghai Chen Hua Instrument Ltd.) to apply-1V of working electrode, continue 3 hours, obtain being grown in ito glass or FTO ZnO nano-rod array on glass; By this ZnO nano-rod array in concentration be 0.2M, temperature be 85 DEG C of sodium hydrate aqueous solutions in soak 1.5 hours, obtain single crystal ZnO nano-tube array.There are the ito glass of single crystal ZnO nano-tube array or FTO glass to be placed in porcelain boat growth, are placed on the low temperature center district of two temperature-area tubular furnaces, place in the high temperature center of tubular furnace the porcelain boat that 2 grams of SnO powder are housed.System is vacuumized with mechanical pump, in system, pass into Ar/H
2combination gas (wherein H
2volume content be 5%), flow is 50sccm.By diamond heating, heating rate is 20 DEG C/min, makes the temperature of high temperature center and low temperature center reach respectively 850 DEG C and 600 DEG C, maintains this temperature after 1 hour, stops heating; Treat that temperature is down to room temperature, take out sample, obtain polycrystalline SnO
2the array of the coated single crystal ZnO nanotube of nano-particular film, and by polycrystalline SnO
2the film that nano particle forms is evenly coated on the inner and outer wall of single crystal ZnO nanotube.By this polycrystalline SnO
2in the Nafion solution that the array of the coated single crystal ZnO nanotube of nano-particular film is 5% in mass concentration, soak after 10 minutes and take out, naturally dry, at ito glass or FTO is on glass obtains vertically growth and have the polycrystalline SnO of Nafion modification
2the array of the coated single crystal ZnO nanotube of nano-particular film.The polycrystalline SnO that prepared Nafion modifies
2pattern and the single polycrystalline SnO of the array of the coated single crystal ZnO nanotube of nano-particular film
2the structural characterization of the coated single crystal ZnO nanotube of nano-particular film respectively as depicted in figs. 1 and 2.The polycrystalline SnO that this Nafion modifies
2the array of the coated single crystal ZnO nanotube of nano-particular film can be used for detecting the dopamine in aqueous solution.
Embodiment 2.
The polycrystalline SnO that is vertically grown in the suprabasil Nafion modification of ito glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 0.1 μ M dopamine.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 3.
Embodiment 3.
The polycrystalline SnO that is vertically grown in the suprabasil Nafion modification of ito glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 2 μ M dopamines.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 4.
Embodiment 4.
The polycrystalline SnO that is vertically grown in the suprabasil Nafion modification of ito glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 10 μ M dopamines.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 5.
Embodiment 5.
The polycrystalline SnO that is vertically grown in the Nafion modification in FTO substrate of glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 100 μ M dopamines.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 6.
Embodiment 6.
The polycrystalline SnO that is vertically grown in the suprabasil Nafion modification of ito glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 500 μ M dopamines.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 7.
Embodiment 7.
The polycrystalline SnO that is vertically grown in the suprabasil Nafion modification of ito glass obtaining with embodiment 1
2the array of the coated single crystal ZnO nanotube of nano-particular film is working electrode, using platinum plate electrode as to electrode, and using saturated calomel electrode as contrast electrode, composition three-electrode electro Chemical system.Detected object is to contain the PBS solution (pH=7.4) that concentration is 0.1～500 μ M dopamine.By electrochemical workstation, utilize the electrochemical response of cyclic voltammetry (CV) and differential pulse execution (DPV) test detected object, result is as shown in Figure 8.
Claims (6)
1. the perfluorinated sulfonic resin for detection of dopamine is modified SnO
2the nanometer pipe array electrode of clading ZnO, is characterized in that: described nanometer pipe array electrode is by conductive substrates and is vertically grown in the polycrystalline SnO that the perfluorinated sulfonic resin in this conductive substrates is modified
2the array of the coated single crystal ZnO nanotube of nano-particular film forms.
2. the perfluorinated sulfonic resin for detection of dopamine according to claim 1 is modified SnO
2the nanometer pipe array electrode of clading ZnO, is characterized in that: described conductive substrates is ito glass or FTO glass.
3. the perfluorinated sulfonic resin for detection of dopamine according to claim 1 is modified SnO
2the nanometer pipe array electrode of clading ZnO, is characterized in that: described polycrystalline SnO
2nano-particular film is coated single crystal ZnO nanotube, is by polycrystalline SnO
2the film that nano particle forms is evenly coated on the inner and outer wall of single crystal ZnO nanotube.
4. the perfluorinated sulfonic resin for detection of dopamine according to claim 1 is modified SnO
2the nanometer pipe array electrode of clading ZnO, is characterized in that: it is by by polycrystalline SnO that described perfluorinated sulfonic resin is modified
2in the perfluor sulfoacid resin solution that the array of the coated single crystal ZnO nanotube of nano-particular film is 5% in mass concentration, soak to realize.
5. the perfluorinated sulfonic resin for detection of dopamine described in claim 1～4 any one is modified SnO
2the application of the nanometer pipe array electrode of clading ZnO, it is characterized in that: described nanometer pipe array electrode is for detecting the dopamine of aqueous solution, using described nanometer pipe array electrode as working electrode, using platinum plate electrode as to electrode, using saturated calomel electrode as contrast electrode, when the dopamine in aqueous solution detection with cyclic voltammetry or differential pulse voltammetry, described nanometer pipe array electrode produces extremely strong electrochemical signals;
The linear response range of cyclic voltammetry is 0.1～500 μ M, and the linear response range of differential pulse voltammetry is 0.1～2 μ M.
6. application according to claim 5, is characterized in that: the concentration of the dopamine in described aqueous solution is that 0.1 μ M is to 500 μ M.
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| CN105514374B (en) * | 2015-12-11 | 2019-01-01 | 武汉理工大学 | A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof |
| CN105671654A (en) * | 2016-01-21 | 2016-06-15 | 合肥工业大学 | Ionic induction type artificial skin array structure and preparation method thereof |
| CN105671654B (en) * | 2016-01-21 | 2018-06-26 | 合肥工业大学 | A kind of ion induction type artificial skin array structure and preparation method thereof |
| CN108254426A (en) * | 2017-12-15 | 2018-07-06 | 新乡医学院 | It is prepared for dopamine concentration detection miniature electrochemical in animal brain |
| CN108288695A (en) * | 2018-01-11 | 2018-07-17 | 中南大学 | A kind of zinc-based secondary battery cathode material and preparation method thereof |
| CN108288695B (en) * | 2018-01-11 | 2020-09-01 | 中南大学 | Zinc-based secondary battery negative electrode material and preparation method thereof |
| CN108717075A (en) * | 2018-05-21 | 2018-10-30 | 大连理工大学 | The method for detecting uric acid using the film modified electrode slice of electro-deposition perfluorinated sulfonic acid |
| CN108717075B (en) * | 2018-05-21 | 2019-05-10 | 大连理工大学 | Utilize the method for the film modified electrode slice detection uric acid of electro-deposition perfluorinated sulfonic acid |
| CN111244399A (en) * | 2018-11-28 | 2020-06-05 | 中南大学 | Metal oxide modified zinc oxide tube composite negative electrode material for zinc secondary battery and preparation method thereof |
| CN111244399B (en) * | 2018-11-28 | 2021-11-26 | 中南大学 | Metal oxide modified zinc oxide tube composite negative electrode material for zinc secondary battery and preparation method thereof |
| CN111678963A (en) * | 2020-06-22 | 2020-09-18 | 南京大学 | Ultra-high-sensitivity dopamine biosensor and preparation method thereof |
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