CN100495736C - Process for producing TiO*/metallic array electrode with ordered nano-structure - Google Patents
Process for producing TiO*/metallic array electrode with ordered nano-structure Download PDFInfo
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- CN100495736C CN100495736C CNB2007100400131A CN200710040013A CN100495736C CN 100495736 C CN100495736 C CN 100495736C CN B2007100400131 A CNB2007100400131 A CN B2007100400131A CN 200710040013 A CN200710040013 A CN 200710040013A CN 100495736 C CN100495736 C CN 100495736C
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Abstract
The present invention belongs to the technical field of electrochemistry relating to a method of producing an ordered nanometer structure TiO2/metal array electrode provided with electric catalysis and photoelectric activation, which is divided into two steps: A TiO2 nanometer tube is prepared through anodic oxidation. Metal is settled in the TiO2 nanometer tube through cathode electrochemical reduction. The TiO2 metal array electrode produced according to the present invention shows obvious positive electrode photoelectric current under irradiation of white rays and is suitable for solar photoelectric conversion and photolytic water, etc. In addition, the electrode brings excellent electric catalysis to methanol electro-oxidation, thus adapting to production methanol fuel-based battery.
Description
Technical field
The invention belongs to the electrochemical techniques technical field, be specifically related to a kind of nano-structural ordered TiO with electro catalytic activity and photoelectric activity
2The preparation method of/metallic array electrode.
Background technology
Found semiconductor titanium dioxide since splitting water into hydrogen and oxygen under the UV-irradiation from 1972, titanium dioxide has been subjected in the material field paying attention to very widely.TiO
2Can be used for many aspects such as photocatalysis to degrade organic matter, sterilizing, sewage disposal, air cleaning and photocatalytic hydrogen production by water decomposition, at present, nanostructure TiO
2Preparation method's research become a very active problem of photocatalysis new material exploitation.Titanium deoxid film preparation technology's research is nano-TiO
2Basis and prerequisite that photocatalysis and opto-electronic conversion are used.Utilize template (as anodic oxidation aluminium formwork) can on the substrate of conduction, prepare TiO by electrochemical deposition technique
2Array film electrode, still, the TiO of ordered nano-structure
2The preparation of/metallic array electrode does not appear in the newspapers.
Summary of the invention
The objective of the invention is to propose a kind of new method for preparing the titanium dioxide/metal array composite film electrode of ordered nano-structure.
The used raw material of the inventive method are metal titanium sheet, and capital equipment has D.C. regulated power supply, potentiostat, and preparation process is seen schematic diagram 1.Preparation process was divided into for two steps:
(1) anode oxidation method prepares TiO
2Nanotube.
With the thickness after cleaning is that 0.1～0.25mm metal titanium sheet is fixed in the electrolytic cell as work electrode, to electrode employing graphite or metal Pt sheet; By lead work electrode with electrode is connected the output of D.C. regulated power supply, two interelectrode distances remain on 2cm, the volumetric concentration of HF solution is 0.1%～0.5% (v/v), the output voltage of regulating D.C. regulated power supply is 10～20V, the control anodizing time is 20-120min, and anodic oxidation obtains TiO to metal titanium sheet
2Nano-tube film.Fig. 2 prepares TiO for anode oxidation method
2The device schematic diagram of nanotube.Fig. 3 is the TiO that obtains
2The SEM image of nano-tube film.
(2) the electrochemical cathode method of reducing is at TiO
2Plated metal in the nanotube.
Electrolyte adopts 1～5mM H
2PtCl
6Solution utilizes potentiostat to pass through constant potential or constant current cathode electrodeposition metal M sedimentation time is 10-90s.Because at TiO
2The nanotube internal barrier is thinner, and electronics can conduct electricity by tunnelling, makes preferentially nucleation in nanotube of metal M to form TiO
2Nanotube/metal M array composite film electrode, the composite array electrode structure is shown in Fig. 1 c.Fig. 4 is TiO
2Nanotube electrode (a) and TiO
2Nanotube/Pt combination electrode (b) is at 1M H
2SO
4Cyclic voltammogram in the solution.Here be that example describes with Pt.In this step, the metal M of deposition can Pt, Au, Ag, Cu or Ni etc.
Experiment shows that ordered nano titanium dioxide/metal array composite film electrode that the new technology that is proposed by the present invention prepares has the feature and the good catalytic action of typical n N-type semiconductor N.
1. under white light, with the ordered nano TiO of new technology preparation
2/ metallic array electrode shows tangible anode photoelectric current, and density of photocurrent is 0.31mA.cm
-2(0.8V), than the TiO that does not have plated metal
2Electrode increases by 1 times.As shown in Figure 5, photovoltage numerical value is with respect to nano-TiO
2Electrode also increases to some extent, and as shown in Figure 6, the numerical value of increase is relevant with the deposition of Pt.The result shows the nano-TiO by this new technology preparation
2Film has the feature of typical n N-type semiconductor N, is applied in can be aspect solar photovoltaic conversion and photodissociation water.
2. the new technology that proposes with the present invention prepares TiO
2/ metallic array electrode shows good catalytic action to methanol electro-oxidizing, as shown in Figure 7.The TiO of the new technology preparation that the present invention proposes
2Film can be applicable to the fuel cell aspect based on methyl alcohol.
Description of drawings
Fig. 1 ordered nano-structure TiO
2The preparation process schematic diagram of/metallic array electrode; A is the metal Ti sheet, and b is Ti/TiO
2Nanotube electrode, c are TiO
2Nanotube electrode and/Pt ordered nano-structure composite array electrode.
Fig. 2 prepares TiO for the anodic titanium sheet
2Nanotube experimental provision schematic diagram,
Fig. 3 is the TiO that the anodic oxidation of titanium sheet forms
2The sem photograph of nanotube
Fig. 4 is TiO
2Nanotube electrode (a) and TiO
2Nanotube/Pt composite array electrode (b) is at 1M H
2SO
4Cyclic voltammogram in the solution.
Fig. 5 is TiO
2Nanotube electrode (a) and TiO
2The photoelectric current of nanotube/Pt composite array electrode (b) is measured, white light, 250mW.cm
-2, 0.5M Na
2SO
4Solution.A ', b ' represent corresponding dark current～potential curve.
Fig. 6 is TiO
2Nanotube electrode (a) and TiO
2The photovoltage of nanotube/Pt composite array electrode (b) is measured, white light, 250mW.cm
-2, 0.5M Na
2SO
4Solution.
Fig. 7 is TiO
2Nanotube/Pt oldered array composite film electrode is to the cyclic voltammogram of the electro-catalysis experiment of methyl alcohol, a, 1MH
2SO
4Solution; B, 1M H
2SO
4Solution+1M CH
3OH.
Number in the figure: 1 is the Ti electrode, and 2 is that 3 is electrolytic cell to electrode (graphite or Pt sheet), and 4 is magnetic stir bar.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1: (thickness is 0.1mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolytic cell as work electrode, by lead work electrode with electrode is connected the output of D.C. regulated power supply, two interelectrode distances remain on 2cm, the HF solution that adds 0.5% (v/v) concentration, the input voltage of regulating D.C. regulated power supply is 20V, the control anodizing time is 40min, and anodic oxidation obtains TiO to metal titanium sheet like this
2Nano-tube film.Electrolyte is changed to 1.25mM H
2PtCl
6Solution is the 1mA cathode electrodeposition by Control current, and sedimentation time is 30s.Ti/TiO
2Nanotube electrode is a work electrode, and the Ag/AgCl electrode is a reference electrode, and the Pt sheet is to electrode.The TiO that obtains
2Nanotube electrode and/Pt nano wire composite array electrode.The Ti/TiO that obtains
2Nanotube electrode and TiO
2Nanotube/Pt composite array electrode is at H
2SO
4Cyclic voltammogram in the solution as shown in Figure 4.The result shows that Pt successfully is deposited on the electrode.
Embodiment 2: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolytic cell as work electrode, by lead work electrode with electrode is connected the output of voltage regulator, two interelectrode distances remain on 2cm, the HF solution that adds 0.5% (v/v), the output voltage of regulating D.C. regulated power supply is 10V, the control anodizing time is 80min, and anodic oxidation obtains TiO to metal titanium sheet
2Nano-tube film.Electrolyte is changed to H
2PtCl
6Solution, by cathode electrodeposition at TiO
2Plated metal Pt in the nanotube, electrodeposition time is 30s.The Ti/TiO that obtains
2Nanotube electrode and TiO
2The photoelectric current test result of nanotube/Pt composite array electrode as shown in Figure 5, the photovoltage test result is as shown in Figure 6.The result shows that the introducing of Pt helps increasing TiO
2The photoelectric current of electrode and photovoltage.
Embodiment 3: (thickness is 0.25mm to the metal titanium sheet after will cleaning, area 1cm
2) be fixed in the electrolytic cell as work electrode, by lead work electrode with electrode is connected the output of D.C. regulated power supply, two interelectrode distances remain on 2cm, the HF solution of adding 0.5%, the output voltage of regulating D.C. regulated power supply is 20V, the control anodizing time is 40min, and anodic oxidation obtains TiO to metal titanium sheet
2Nano-tube film.Electrolyte is changed to H
2PtCl
6Solution is at TiO
2Plated metal Pt in the nanotube, electrodeposition time is 60s, the TiO that obtains
2Nanotube/Pt composite array electrode.To the electro catalytic activity of methyl alcohol as shown in Figure 7, (a) is at 1M H among the figure
2SO
4Cyclic voltammogram in the solution; (b) be at 1M H
2SO
4Solution+1M CH
3Cyclic voltammogram among the OH.As can be seen from Figure 7, TiO
2Nanotube/Pt composite array electrode pair methyl alcohol shows good electro catalytic activity.
Claims (1)
1, a kind of ordered nano-structure TiO
2The preparation method of/metallic array electrode is characterized in that concrete steps are as follows:
(1) the anode chlorination prepares TiO
2Nanotube
Thickness after cleaning is fixed in the electrolytic cell as work electrode, to electrode employing graphite or metal Pt sheet for the 0.1-0.25mm metal titanium sheet; By lead work electrode with electrode is connected the output of D.C. regulated power supply, two interelectrode distances remain on 2cm, the volumetric concentration of the HF solution in the described electrolytic cell is 0.1%-0.5%, the output voltage of regulating D.C. regulated power supply is 10-20V, the control anodizing time is 20-120min, and anodic oxidation obtains TiO to metal titanium sheet
2Nano-tube film;
(2) the electrochemical cathode method of reducing is at TiO
2Plated metal in the nanotube
Electrolyte adopts 1-5mM H
2PtCl
6Solution utilizes potentiostat to pass through constant potential or constant current cathode electrodeposition metal M sedimentation time is 10-90s, makes metal M nucleation in nanotube to form TiO
2Nanotube/metal M array composite film electrode; Wherein Chen Ji metal M is Pt, Au, Ag, Cu or Ni.
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| CNB2007100400131A CN100495736C (en) | 2007-04-26 | 2007-04-26 | Process for producing TiO*/metallic array electrode with ordered nano-structure |
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| CNB2007100400131A CN100495736C (en) | 2007-04-26 | 2007-04-26 | Process for producing TiO*/metallic array electrode with ordered nano-structure |
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| CN100495736C true CN100495736C (en) | 2009-06-03 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101303325B (en) * | 2008-06-25 | 2011-03-30 | 华东师范大学 | Method for preparing platinum nanometer perforated electrodes with electrodeposition |
| CN101665902B (en) * | 2008-09-03 | 2011-03-16 | 中国科学院合肥物质科学研究院 | Nickel ordered porous array film and preparation method thereof |
| JP2011014356A (en) * | 2009-07-01 | 2011-01-20 | Sony Corp | Photoelectric conversion element, method of manufacturing therefor, and electronic device |
| CN101613080B (en) * | 2009-07-23 | 2011-03-23 | 重庆大学 | Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN101857288B (en) * | 2010-06-18 | 2011-10-26 | 南京理工大学 | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode |
| CN101908477B (en) * | 2010-08-02 | 2011-12-07 | 复旦大学 | Method for preparing gate stack of metallic nano crystal memory |
| CN102247828B (en) * | 2011-05-13 | 2012-12-26 | 西北有色金属研究院 | Hydrotreated TiO2 nanotube array and preparation method thereof |
| CN102324306A (en) * | 2011-06-21 | 2012-01-18 | 中国科学院理化技术研究所 | Dye-sensitized solar cell working electrode and preparation method that nano silver wire mixes |
| CN102277609A (en) * | 2011-08-02 | 2011-12-14 | 复旦大学 | Preparation method of carbon-nitrogen co-doped TiO2 nano-tube thin film with visible light activity |
| CN102352524B (en) * | 2011-09-21 | 2014-04-23 | 浙江工商大学 | Metal oxide modified TiO2 nanometer tube array electrode and preparation method thereof |
| CN102544182B (en) * | 2012-01-05 | 2014-07-16 | 西北工业大学 | Surface plasmon resonance rectenna and preparation method therefor |
| CN104404565B (en) * | 2014-11-13 | 2016-08-24 | 苏州大学 | Au/TiO2optoelectronic pole of nanotube composite construction and preparation method thereof |
| US9567677B2 (en) | 2015-04-07 | 2017-02-14 | King Saud University | Electrochemical method of producing hydrogen peroxide using a titanium oxide nanotube catalyst |
| CN108538604A (en) * | 2018-04-02 | 2018-09-14 | 深圳汇创联合自动化控制有限公司 | A kind of solar cell module |
| CN108443807A (en) * | 2018-04-02 | 2018-08-24 | 深圳凯达通光电科技有限公司 | One kind being based on the energy-saving and environment-friendly intelligent road-lamp of Internet of Things |
| CN111744471B (en) * | 2020-08-04 | 2023-01-24 | 郑州大学 | Method for preparing self-supporting titanium dioxide supported noble metal catalyst |
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