CN105021676A - Titanium dioxide microsphere modified electrode with three-dimensional dandelion-like hierarchical structure, and preparation method and application thereo - Google Patents
Titanium dioxide microsphere modified electrode with three-dimensional dandelion-like hierarchical structure, and preparation method and application thereo Download PDFInfo
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- CN105021676A CN105021676A CN201510395477.9A CN201510395477A CN105021676A CN 105021676 A CN105021676 A CN 105021676A CN 201510395477 A CN201510395477 A CN 201510395477A CN 105021676 A CN105021676 A CN 105021676A
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Abstract
The invention discloses a titanium dioxide microsphere modified electrode with three-dimensional dandelion-like hierarchical structure, and a preparation method and application thereof. The titanium dioxide material comprises a plurality of titanium dioxide microspheres with three-dimensional dandelion-like hierarchical structure, emitting from the center and in radiating shape. The preparation of the electrode comprises the steps of: uniformly mixing isopropyl titanate, hydrochloric acid, cetyl trimethyl ammonium bromide with deionized water, conducting a hydrothermal reaction with ethylene glycol at a certain temperature, centrifuging, washing and drying; then subjecting titanium dioxide to ultrasonic dispersion into the polyethylene oxide gel; and finally apply the dispersed liquid to the activated screen-printed electrode surface and drying at room temperature. The titanium dioxide / screen printing electrode has high specific surface area, many active sites and high electron transfer rate; and the modified electrode can be used to detect sunset yellow, and has the characteristics of fast response time, good reproducibility and high stability.
Description
Technical field
The invention belongs to three-dimensional hierarchical structure material modified electrode field, be specially a kind of preparation method and application thereof of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode.
Background technology
In the past few decades, due to the physicochemical property of uniqueness and the application in photoelectric device, catalyzer, lithium ion battery and sensor, three-dimensional hierarchical structure has caused considerable concern.The simplest route of synthesis of three-dimensional hierarchical structure is exactly self assembly, i.e. the process of the spontaneous formation of ordered aggregation.Therefore, much research in recent years concentrates on and the nano material of one dimension, two-dimensional structure (as nano wire, nanometer rods and nanometer sheet etc.) is self-assembled into more complicated orderly hierarchy, thus acquisition has higher surface-to-volume ratio, the nano material of the character of intrinsic anisotropy and adjustable space distribution.At present, a lot of method has been had to be used for preparing the nano material with hierarchy, comprising low-temperature aqueous solution method, the precipitation method, phonochemistry method, hydro-thermal method.In above method, due to hydro-thermal method have synthesis condition gentleness, financial cost low, be easy to the advantages such as operation, be widely used in preparing various hierarchical structure nano material.
As a kind of semiconductor material, titania has the performance of many excellences, thus makes it be widely used in photoelectric cell, photocatalysis and electrochemical sensor field.In recent years, due to the impact of quantum size effect and high-specific surface area, the surface nature of titanium dioxide nano material is subject to the control of its structure and dimension to a great extent, thus existing large quantifier elimination concentrates on the configuration of surface controlling titanium dioxide nano material, especially three-dimensional hierarchical structure titanium dioxide nano material.Therefore, three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere is modified on electrode and goes, larger specific surface area can be made it have, thus improve the combination property of electrode, comprise electric conductivity, catalytic performance and sensitivity etc.
Therefore, prepare three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode, use it for the quick detection of sunset yellow, there is good application prospect in Food Monitoring.
Summary of the invention
The object of the invention is to by preparing a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere, thus the preparation method of the three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode that a kind of response time is fast, favorable reproducibility, stability are high is provided.
Another object of the present invention is to provide the preparation method of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode the application in sunset yellow detects.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode, is characterized in that, comprise the following steps:
(1) preparation of titanium dioxide nano material
Will containing titanium precursors, hydrochloric acid and cetyl trimethyl ammonium bromide Homogeneous phase mixing in deionized water, then gained potpourri and ethylene glycol being placed in pressure is that the autoclave of 2 ~ 3MPa reacts 12 ~ 20 hours in 150 ~ 200 DEG C; After cooling, lower sediment is got in centrifuging, through deionized water and ethanol washing, dry, obtains titanium dioxide nano material;
(2) preparation of titanium oxide dispersion
By titanium dioxide nano material ultrasonic disperse in gel, obtain titanium oxide dispersion;
(3) preparation of titania/screen printing electrode
Step (2) gained titanium oxide dispersion is dripped on the screen printing electrode being applied to activated process, drying at room temperature, obtain titania/screen printing electrode and be sunset yellow detecting electrode.
In step (3), the screen printing electrode of described activation process obtains by the following method: in electrochemical workstation, the contrast electrode of screen printing electrode is as contrast electrode, the working electrode of screen printing electrode is as working electrode, screen printing electrode to electrode as to electrode, adopt cyclic voltammetry scanning sulfuric acid solution, the concentration of sulfuric acid solution is 0.1 ~ 1M, the potential range of cyclic voltammetry scan sulfuric acid solution is-1.0 ~ 1.0V, sweep speed is 10 ~ 100mV/s, and the scanning number of turns is 1 ~ 20 circle.
Containing titanium precursors described in step (1) is isopropyl titanate.
Deionized water described in step (1), hydrochloric acid, cetyl trimethyl ammonium bromide and the mol ratio containing titanium precursors are 100:7:0.03:0.03 ~ 0.05.
Described in step (1), the volume ratio of potpourri and ethylene glycol is 1:0 ~ 2.
According to the ratio adding 4g titanium dioxide nano material in every 1 ~ 2L gel in step (2), by titanium dioxide nano material ultrasonic disperse in gel, described gel is polyoxyethylene aqueous solution.
It is 8 ~ 12 μ L that titanium oxide dispersion described in step (3) drips painting amount.
Compared with prior art, tool of the present invention has the following advantages:
The first, the present invention uses titania as electrode sensitive material, gained titania/screen printing electrode stable performance, and the response time is fast and with low cost, has good application prospect;
The second, the present invention adopts a coating method directly titanium oxide dispersion to be coated on electrode surface and obtains sensitive membrane, and operation is simple, favorable reproducibility;
3rd, the present invention adopts three-dimensional dandelion shape hierarchy titanium dioxide nano material as electrode material, can obtain the electrode of high-specific surface area, substantially increase the sensitivity of electrode;
4th, electrode prepared by the present invention can detect sunset yellow fast, delicately, can be applicable to different foodstuff samples.
Accompanying drawing explanation
Fig. 1 is 20000 times of SEM figure of titania/screen printing electrode in embodiment 1;
Fig. 2 is 50000 times of SEM figure of titania/screen printing electrode in embodiment 1;
Fig. 3 is 30000 times of SEM figure of titania/screen printing electrode in embodiment 2;
Fig. 4 is 20000 times of SEM figure of titania/screen printing electrode in embodiment 3;
Fig. 5 is the CV figure that titania in embodiment 1,2 and 3/screen printing electrode detects sunset yellow.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.The screen printing electrode used in following examples is purchased from Suzhou company limited of Yangtze River Delta system biological interdisciplinary science research institute; Cetyl trimethyl ammonium bromide and ethylene glycol are purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Isopropyl titanate and sunset yellow are purchased from Aladdin.
In embodiment, electrode used therein is screen printing electrode, and screen printing electrode carried out following activation process before dripping painting titanium oxide dispersion:
In electrochemical workstation, the contrast electrode of screen printing electrode is as contrast electrode, the working electrode of screen printing electrode is as working electrode, screen printing electrode to electrode as to electrode, speed of sweeping with 50 mV/s under-1.0 ~ 1.0 V current potentials scans 0.5 M sulfuric acid solution, scanning 10 circle, the electrode ambient temperatare after activation puts drying.
embodiment 1
A preparation method for titania/screen printing electrode, step is as follows:
The ratio uniform being 100:7:0.03:0.05 in molar ratio with isopropyl titanate by deionized water, hydrochloric acid, cetyl trimethyl ammonium bromide mixes, then the ratio being 1:2 by volume by potpourri and ethylene glycol is placed in the teflon autoclave (100ml) that pressure is 2 ~ 3MPa, react 20 hours at 150 DEG C, lower sediment is got after cooling, centrifuging, after deionized water and ethanol washing, dry 24h obtains titanium dioxide nano material at 60 DEG C in an oven.
By the titanium dioxide nano material ultrasonic disperse of 4.0mg in the polyoxyethylene gel of 1mL, obtain homodisperse titanium oxide dispersion, then dripped by the titanium oxide dispersion of 8 μ L and be coated onto screen printing electrode surface, under room temperature, drying obtains titania/screen printing electrode.
Fig. 1, Fig. 2 are the scanning electron microscope (SEM) photograph of titania/screen printing electrode under different multiplying that the present embodiment obtains, as can be seen from Fig., three-dimensional dandelion shape titanium dioxide microballoon sphere particle diameter is about 4 μm, titanium dioxide nano thread by manyly sending from center, is radially formed, the diameter of nano wire is about 10nm, and length is about 1.5 μm.This structure has larger specific surface area, can provide more avtive spot, accelerates electron transport rate, improves catalytic activity.
embodiment 2
A preparation method for titania/screen printing electrode, step is as follows:
The ratio uniform being 100:7:0.03:0.04 in molar ratio with isopropyl titanate by deionized water, hydrochloric acid, cetyl trimethyl ammonium bromide mixes, then the ratio being 1:1 by volume by potpourri and ethylene glycol is placed in the teflon autoclave (100ml) that pressure is 2 ~ 3MPa, react 16 hours at 180 DEG C, lower sediment is got after cooling, centrifuging, after deionized water and ethanol washing, dry 24h obtains titanium dioxide nano material at 60 DEG C in an oven.
By the titanium dioxide nano material ultrasonic disperse of 4.0mg in the polyoxyethylene gel of 1.5mL, obtain homodisperse titanium oxide dispersion, then dripped by the titanium oxide dispersion of 10 μ L and be coated onto screen printing electrode surface, under room temperature, drying obtains titania/screen printing electrode.
Fig. 3 is the scanning electron microscope (SEM) photograph of titania/screen printing electrode that the present embodiment obtains, as can be seen from Fig., three-dimensional titanium dioxide microballoon sphere particle diameter is about 3 μm, titanium dioxide nano-rod by sending from center a little, is radially formed, the diameter of nanometer rods is about 100nm, and length is about 1.2 μm.
embodiment 3
A preparation method for titania/screen printing electrode, step is as follows:
The ratio uniform being 100:7:0.03:0.03 in molar ratio with isopropyl titanate by deionized water, hydrochloric acid, cetyl trimethyl ammonium bromide mixes, then the ratio being 1:0 by volume by potpourri and ethylene glycol is placed in the teflon autoclave (100ml) that pressure is 2 ~ 3MPa, react 12 hours at 200 DEG C, lower sediment is got after cooling, centrifuging, after deionized water and ethanol washing, dry 24h obtains titanium dioxide nano material at 60 DEG C in an oven.
By the titanium dioxide nano material ultrasonic disperse of 4.0mg in the polyoxyethylene gel of 2mL, obtain homodisperse titanium oxide dispersion, then dripped by the titanium oxide dispersion of 12 μ L and be coated onto screen printing electrode surface, under room temperature, drying obtains titania/screen printing electrode.
Fig. 4 is the scanning electron microscope (SEM) photograph of titania/screen printing electrode that the present embodiment obtains, and as can be seen from Fig., three-dimensional titanium dioxide microballoon sphere particle diameter is about 4 μm, surface smoothing.
embodiment 4
Titania/screen printing electrode that embodiment 1 ~ 3 obtains is to the Electrochemical Detection of sunset yellow:
Sunset yellow is dissolved in the sulfuric acid solution of 0.1M the solution being mixed with 1.0 μMs, and in solution, leads to oxygen to state of saturation.The contrast electrode of the titania/screen printing electrode obtained by embodiment 1 ~ 3 is as contrast electrode, titania/screen printing electrode to electrode as to electrode, the working electrode of titania/screen printing electrode is as working electrode, adopt cyclic voltammetry (CV) to scan sunset yellow solution, scanning potential range is-0.3 ~ 0.4 V.
Fig. 5 is the CV figure of titania/screen printing electrode detection sunset yellow that embodiment 1 ~ 3 obtains, obtained by map analysis, obvious reduction peak is not observed (curve a) when detecting with screen printing electrode, and all can observe obvious reduction peak when detecting with titania/screen printing electrode that embodiment 1 ~ 3 is obtained, and the reduction peak current maximum (curve d) of the obtained three-dimensional dandelion shape titanium dioxide microballoon sphere modified electrode of embodiment 1, embodiment 2 next (curve c), embodiment 3 minimum (curve b).
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a preparation method for three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode, is characterized in that, comprise the following steps:
(1) preparation of titanium dioxide nano material
Will containing titanium precursors, hydrochloric acid and cetyl trimethyl ammonium bromide Homogeneous phase mixing in deionized water, then gained potpourri and ethylene glycol being placed in pressure is that the autoclave of 2 ~ 3MPa reacts 12 ~ 20 hours in 150 ~ 200 DEG C; After cooling, lower sediment is got in centrifuging, through deionized water and ethanol washing, dry, obtains titanium dioxide nano material;
(2) preparation of titanium oxide dispersion
By titanium dioxide nano material ultrasonic disperse in gel, obtain titanium oxide dispersion;
(3) preparation of titania/screen printing electrode
Step (2) gained titanium oxide dispersion is dripped on the screen printing electrode being applied to activated process, drying at room temperature, obtain titania/screen printing electrode and be sunset yellow detecting electrode.
2. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1, it is characterized in that, in step (3), the screen printing electrode of described activation process obtains by the following method: in electrochemical workstation, the contrast electrode of screen printing electrode is as contrast electrode, the working electrode of screen printing electrode is as working electrode, screen printing electrode to electrode as to electrode, adopt cyclic voltammetry scanning sulfuric acid solution, the concentration of sulfuric acid solution is 0.1 ~ 1M, the potential range of cyclic voltammetry scan sulfuric acid solution is-1.0 ~ 1.0V, sweep speed is 10 ~ 100mV/s, the scanning number of turns is 1 ~ 20 circle.
3. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1 and application thereof, is characterized in that, is isopropyl titanate containing titanium precursors described in step (1).
4. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1 and application thereof, it is characterized in that, deionized water described in step (1), hydrochloric acid, cetyl trimethyl ammonium bromide and the mol ratio containing titanium precursors are 100:7:0.03:0.03 ~ 0.05.
5. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1 and application thereof, it is characterized in that, described in step (1), the volume ratio of potpourri and ethylene glycol is 1:0 ~ 2.
6. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1 and application thereof, it is characterized in that, according to the ratio adding 4g titanium dioxide nano material in every 1 ~ 2L gel in step (2), by titanium dioxide nano material ultrasonic disperse in gel, described gel is polyoxyethylene aqueous solution.
7. the preparation method of a kind of three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode according to claim 1 and application thereof, it is characterized in that, it is 8 ~ 12 μ L that titanium oxide dispersion described in step (3) drips painting amount.
8. the application of preparation method in sunset yellow detects of the three-dimensional dandelion shape hierarchy titanium dioxide microballoon sphere modified electrode described in claim 1-6 any one.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11326272A (en) * | 1999-03-18 | 1999-11-26 | Agency Of Ind Science & Technol | Visible light-responsive electrode |
| US6838054B1 (en) * | 1998-04-17 | 2005-01-04 | Imperial College Of Science, Technology And Medicine | Biochemical devices and their methods of manufacture |
| CN102854234A (en) * | 2012-07-23 | 2013-01-02 | 常州大学 | Detection method of sunset yellow in food |
| CN103675048A (en) * | 2013-11-18 | 2014-03-26 | 西安交通大学 | Metal-oxide gas sensor based on MEMS (Micro-Electro-Mechanic System) and preparation technology thereof |
| CN103743802A (en) * | 2014-01-10 | 2014-04-23 | 南京师范大学 | DNA biosensor based on three-dimensional ordered gold doped nano titanium dioxide electrode as well as preparation method and application of DNA biosensor |
| CN104698053A (en) * | 2015-03-30 | 2015-06-10 | 河海大学 | Titanium dioxide-carbon rod microelectrode, preparation method and application thereof for detecting concentration of acetaminophen in blood |
-
2015
- 2015-07-07 CN CN201510395477.9A patent/CN105021676A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6838054B1 (en) * | 1998-04-17 | 2005-01-04 | Imperial College Of Science, Technology And Medicine | Biochemical devices and their methods of manufacture |
| JPH11326272A (en) * | 1999-03-18 | 1999-11-26 | Agency Of Ind Science & Technol | Visible light-responsive electrode |
| CN102854234A (en) * | 2012-07-23 | 2013-01-02 | 常州大学 | Detection method of sunset yellow in food |
| CN103675048A (en) * | 2013-11-18 | 2014-03-26 | 西安交通大学 | Metal-oxide gas sensor based on MEMS (Micro-Electro-Mechanic System) and preparation technology thereof |
| CN103743802A (en) * | 2014-01-10 | 2014-04-23 | 南京师范大学 | DNA biosensor based on three-dimensional ordered gold doped nano titanium dioxide electrode as well as preparation method and application of DNA biosensor |
| CN104698053A (en) * | 2015-03-30 | 2015-06-10 | 河海大学 | Titanium dioxide-carbon rod microelectrode, preparation method and application thereof for detecting concentration of acetaminophen in blood |
Non-Patent Citations (2)
| Title |
|---|
| ZIQI SUN等: "Rational Design of 3D Dendritic TiO2 Nanostructures with Favorable Architectures", 《JUORNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 许娟: "纳米TiO2修饰电极的制备及其应用进展", 《广东化工》 * |
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