CN106958033B - Magn é li phase TinO2n-1The preparation method of nanotube electrode - Google Patents

Magn é li phase TinO2n-1The preparation method of nanotube electrode Download PDF

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CN106958033B
CN106958033B CN201710176005.3A CN201710176005A CN106958033B CN 106958033 B CN106958033 B CN 106958033B CN 201710176005 A CN201710176005 A CN 201710176005A CN 106958033 B CN106958033 B CN 106958033B
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electrode
magn
phase
nanotube
preparation
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CN106958033A (en
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周明华
蔡静菊
梁亮
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Nankai University
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

Magn é li phase Ti is prepared the present invention relates to a kind ofnO2n‑1The method of nanotube electrode.This method is respectively anode and cathode in NH with titanium plate4F‑H2In O-EG solution, the TiO of anodizing preparation is utilized under 40-60V voltage2Nanotube is substrate, restores the Ti of substrate preparation at 750-950 DEG C using hydrogen and nitrogennO2n‑1Nanotube electrode.Its prominent characteristic is that preparation cost is low, and oxidation-reduction potential is high.

Description

Magn é li phase TinO2n-1The preparation method of nanotube electrode
Technical field
The invention belongs to field of environment engineering technology, it is related to a kind of preparing Magn é li phase TinO2n-1The side of nanotube electrode Method.
Background technique
The intermediate product (.OH) or object that electrochemical oxidation is electrolysed by its oxidant source in hydrone are directly in electrode Surface oxidation can complete the degradation of pollutant without adding other reagents by adjusting current potential, be a kind of efficient, green Method.Ideal anode material should analyse oxygen voltage height, conduct electricity very well, acid-alkali-corrosive-resisting, electro catalytic activity height etc..Most often at present Electrode has noble metal electrode, carbon pole and metal oxide electrode etc..Though noble metal electrode electric conductivity is good, price Valuableness limits its application.The most commonly used is titanium supported oxide electrodes for metal oxide electrode, mainly include titanium-based PbO2Electrode, titanium Base SnO2Electrode and titanium-based RuO2Electrode etc..Titanium-based PbO2Though electrode has compared with oxygen evolution potential and electro catalytic activity, it is being electrolysed When be likely to result in lead and dissolve out to form secondary pollution.Titanium-based SnO2Electrode electro Chemical property stablizes but resistivity height and electrode longevity It orders short.
In recent years, boron-doped diamond electrode (BDD) adsorbs inertia and anti pollution property by wide due to analysis oxygen voltage height General application.But the preparation process of BDD electrode is complicated, higher cost limits its application in actual waste water.Magné The sub- titanium oxide Ti of li phasenO2n-1(3 < n < 10) because have and the comparable electric conductivity of graphite, wherein with Ti4O7Conductivity highest, Ti5O9Take second place, analysis oxygen voltage is high, and the characteristics such as acid-alkali-corrosive-resisting receive more and more attention.Prepare TinO2n-1Common method Have with TiO2For presoma, pass through H2It is restored at 1050 DEG C, or in N2In calcine TiO at 1000 DEG C2With the mixed gel of Ti Deng.Since these methods are usually to prepare under conditions of being higher than 1000 DEG C, particle sintering and model deformation are easily caused.Nano junction The sub- titanium oxide substance large specific surface area of structure, it is possible to provide more catalytic sites seek that a kind of preparation condition is relatively mild to be received The sub- Titanium oxide electrode of rice structure has very important practical significance.
Summary of the invention
The purpose of the present invention is prepare orderly Ti by a kind of relatively mild condition that comparesnO2n-1Nano-tube array Electrode.
Preparation condition of the present invention is as follows: using titanium plate as anode, using anodizing in the case where voltage is 40-60V, and electrolyte Group becomes 0.25wt%NH4F-2%wtH21h is electrolysed under conditions of O-EG, through calcining 2h at 450 DEG C into TiO2Nanotube, into one Step is in H2∶N2=1: 5-2: 4, under conditions of flow velocity is 80-120ml/min, 15-60min is restored at 750-950 DEG C and is prepared TinO2n-1Nanotube electrode.
The present invention have outstanding feature below and the utility model has the advantages that
(1) the relatively mild temperature of this method preparation condition is at 1000 DEG C or less.
(2) Ti with nano tube structure is preparednO2n-1。
Detailed description of the invention
Fig. 1 is TiO2The SEM figure of nanotube reduction front and back.
Fig. 2 is TinO2n-1The XRD diagram of nanotube electrode.
Specific embodiment
The present invention is described in further detail by following embodiment combination attached drawing.
(1) method treatment process of the invention
It is respectively anode and cathode with titanium plate (1.5 × 2cm), under conditions of voltage is 40V, the group of electrolyte becomes 0.25%wtNH4F-2%wtH2O-EG is electrolysed 1h, then at 450 DEG C, calcines 2h.With the TiO calcined2Nanotube is base Bottom, in H2∶N2=1: 5, under conditions of flow velocity is 120ml/min, temperature is 950 DEG C, restores 30min, is taken out after then cooling down.
(2) the obtained effect of the embodiment
The example has been TiO2The SEM of nanotube schemes, as shown in Figure 1.It can be found that raw by the titanium plate after anodic oxidation It is up to 14.78 μm of array at marshalling and the length of nanotube, still there is the generation of nanotube after restoring in hydrogen.
Fig. 2 is the XRD diagram of the nanotube after the reduction under different temperatures.Different objects is obtained after different temperature reductions Matter, by comparison, it was found that there is generation Ti6O11And Ti5O9Sub- titanium oxide substance.

Claims (3)

1. a kind of prepare Magn é li phase TinO2n-1The method of nanometer pipe array electrode, it is characterised in that the preparation condition of this method As follows: using titanium plate as anode, control anode voltage is 40-60V, becomes 0.25wt%NH in electrolyte group4F-2%wtH2O-EG Under conditions of be electrolysed 1h, through at 450 DEG C calcine 2h prepare TiO2Nano-tube array, then in H2And N2Gaseous mixture in, control Flow velocity and 750-950 DEG C of temperature restore 10-60min.
2. method according to claim 1, it is characterised in that the H2And N2Mixed proportion be 1/5-2/4.
3. method according to claim 1, it is characterised in that the flow velocity is 80-120ml/min.
CN201710176005.3A 2017-03-17 2017-03-17 Magn é li phase TinO2n-1The preparation method of nanotube electrode Active CN106958033B (en)

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CN107904645B (en) * 2017-10-19 2019-10-11 天津大学 A kind of anodized surface processing method improving metal molybdenum foil surface-active
JP7092076B2 (en) * 2018-03-12 2022-06-28 三菱マテリアル株式会社 Titanium base material, manufacturing method of titanium base material, electrode for water electrolysis, water electrolysis device
CN111762811B (en) * 2019-04-02 2021-06-15 中国科学院上海硅酸盐研究所 Method for preparing black titanium oxide loaded conductive TiO with specific proportion by disproportionating and decomposing titanium suboxide
CN111762812B (en) * 2019-04-02 2021-06-15 中国科学院上海硅酸盐研究所 Method for regulating disproportionation, decomposition and conversion rate of titanium suboxide by temperature
CN110655151A (en) * 2019-10-09 2020-01-07 江西省科学院应用物理研究所 Preparation method of titanium-based titanium suboxide porous electrode
CN110820030B (en) * 2019-11-14 2021-06-15 西安建筑科技大学 Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method
CN113061926A (en) * 2019-12-14 2021-07-02 中国科学院大连化学物理研究所 Titanium dioxide anode diffusion layer for PEM water electrolysis cell and preparation method and application thereof
CN111186883B (en) * 2020-01-09 2021-08-24 青岛理工大学 Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube

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