CN102534723B - Preparation method for ultrafast anode self-assembly double-pass porous nanometer ternary oxide and products prepared through same and purpose of products - Google Patents
Preparation method for ultrafast anode self-assembly double-pass porous nanometer ternary oxide and products prepared through same and purpose of products Download PDFInfo
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- CN102534723B CN102534723B CN201110390539.9A CN201110390539A CN102534723B CN 102534723 B CN102534723 B CN 102534723B CN 201110390539 A CN201110390539 A CN 201110390539A CN 102534723 B CN102534723 B CN 102534723B
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Abstract
The invention discloses a preparation method for an ultrafast anode self-assembly double-pass porous nanometer Ti-Nb-O ternary oxidation film and products prepared through the same and a purpose of the products. A binary titanium alloy serves as an anode, graphite or platinum is a counter electrode, a two-electrode electrolysis method is adopted, anodic oxidization is conducted for 1-30min under the voltage of 10-100 V in an electrolyte containing strong oxidizing substance, and a double-pass porous nanometer ternary oxide amorphous oxidation film is obtained. The surface and the bottom face of the oxidation film are both of a nanometer porous structure. After the double-pass porous nanometer ternary oxide amorphous oxidation film is heat-treated for 30-180min at a temperature ranging from 400-1,000 DEG C, and the double-pass porous nanometer ternary oxidation film with certain crystalline phase composition is obtained. The double-pass porous nanometer ternary porous nanometer oxidation film is high in stability, simple in device requirements, low in cost, capable of being widely applied to fields of photoelectrocatalysis, photoelectrolysis, water pollution treatment, sensors and the like.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to a kind of preparation method of ultrafast anode self-assembly bilateral porous nano ternary oxide and obtained product thereof and purposes.
Background technology
Titanium dioxide is a kind of wide bandgap semiconductor, and stable in properties is nontoxic, has good photoelectricity, photosensitive air-sensitive, pressure-sensitive character.Its photocatalysis characteristic can remove the hazardous and noxious substances of bio-refractory; provide and be considered to a kind of environmental pollution advanced purification technology having future; photocatalytic water liberation of hydrogen and light transfer characteristic, for development of new clean energy, solve worldwide energy dilemma and are of great immediate significance.
TiO
2the preparation of nanotube has template, chemical method and electrochemistry anodic oxidation.Wherein because electrochemistry anodic oxidation can control nanotube pattern and size by preparation parameter, widely adopted.But TiO prepared by common anode oxidation style
2nano structure membrane has multiple restriction in application: the first, due to TiO prepared by anonizing
2nano-tube film is attached to metal base surface, and suitable etchant or high-voltage just can open TiO
2bottom, CN101550581A discloses a kind of bilateral TiO
2the preparation method of film of Nano tube array, utilizes pickling to fall bottom barrier, and process is complicated and perforate is uneven; The second, TiO prepared by common anode oxidation style
2nano-tube film growth velocity is no more than 100nm/h, and this is due in fluorine-containing electrolytic solution, and electrolytic solution is to the TiO generated
2the chemical corrosion rate at nanotube top is very fast, thus limits the length of nanotube, although change electrolyte solution and concentration, growth velocity can reach 13 μm/min, and repeatability is still disputable, and this is to TiO
2be applied to photoelectrocatalysis and solar cell is quite unfavorable; Three, TiO
2be wide-band gap material, need can make TiO by the doping of metallic element or non-metallic element
2forbidden band is reduced to visible-range, increases it and utilizes scope, and such as CN102145294A discloses a kind of ternary TiO
2the preparation method of film, adopts nitriding and differential arc oxidization technique to grow TiO on titanium alloy
2film, CN101157021A disclose a kind of preparation method of visible light active nitrogen doping nanometer titania.
Therefore, prepare dual channel structure titania composite oxide rapidly, and keep nano-porous structure, titanium base TiO can be affected undoubtedly
2the performance such as photoelectricity, catalysis, photoelectrolysis of nano material, and affect the application of its related fields.
Summary of the invention
The object of the invention is to the deficiency preparing vesicular structure technology for existing electrochemical anodic oxidation, a kind of preparation method of ultrafast anode self-assembly bilateral porous nano ternary oxide and obtained product thereof and purposes are provided.
For solving above technical problem, technical scheme of the present invention is: a kind of preparation method of ultrafast anode self-assembly bilateral porous nano ternary oxide, comprises the following steps:
1) pre-treatment of Binary Titanium Alloys: Binary Titanium Alloys is carried out spark cutting, then uses the liquid honing of 200#, 400# to surface smoothing; Afterwards in 10 ~ 20g/l NaOH solution, at 80 ~ 100 DEG C, soak 30 ~ 60min oil removing; Again under ultrasound condition, use acetone and washed with de-ionized water successively, then drying for standby;
2) preparation of electrolytic solution: by oxidizing species and deionized water proportioning in proportion;
3) bilateral porous nano amorphous ternary oxide compound is prepared at alloy surface: adopt two electrode electrolytic pools at normal temperatures, take Binary Titanium Alloys as anode, graphite or platinized platinum are to electrode, under 10 ~ 100V voltage conditions, carry out anodic oxidation 1 ~ 30min, obtain bilateral porous nano ternary amorphous oxides;
4) Crystallizing treatment: heat-treated by bilateral porous nano ternary amorphous oxides, obtains the bilateral porous nano ternary oxide with certain crystalline phase composition.
Described oxide compound is the oxide film on microcosmic with bilateral, nano-porous structure.
Described step 1) interalloy is the alloy Ti-xNb of uniform ingredients, x is the atomic percentage conc of Nb, is preferably 30 ~ 70.
Described step 2) in oxidizing species be superoxide or containing the oxygen acid of Strong oxdiative ability and salt thereof.
Described oxidizing species is preferably perchloric acid and salt, permanganic acid and salt, nitric acid and salt.
Described step 2) in electrolytic solution electrolytical concentration of volume percent be 1 ~ 100vol%.
Described step 3) in oxide compound generating rate be greater than 3g/h.
Described step 4) in thermal treatment temp be 400 ~ 1000 DEG C, thermal treatment be the time is 30 ~ 180min, sintering atmosphere is oxygen atmosphere or air atmosphere.
Described step 4) in the crystalline phase of bilateral porous nano ternary oxide, the crystalline phase composition of its titanium dioxide can be Anatase, Rutile Type or its combination, and the crystalline phase of its niobium oxides can be monoclinic phase or six side's phases or its combination.
The bilateral porous nano ternary oxide product that above-mentioned preparation method obtains, described oxide surface and bottom surface are all in nano-porous structure, and surface apertures 10 ~ 60nm, aperture, bottom surface 20 ~ 100nm, pitch of holes 10 ~ 150nm, nanotube length-to-diameter ratio is greater than 1000.
The purposes of above-mentioned bilateral porous nano ternary oxide product, described ternary oxide product may be used for photoelectricity, catalysis, water pollutions process, sensor field.
Compared with prior art, bilateral porous nano ternary oxide of the present invention has following advantage:
1) utilize titanium alloy to become to be grouped into uniformly and phase composite, carry out TiO
2in-situ dopedly prepare ternary oxide.
2) do not select fluorine-containing solution, prepare high length-diameter ratio nano-porous materials rapidly.
3) single stage method electrochemical anodic oxidation is adopted to obtain bi-pass nano pipe.
4) product can be applicable to the fields such as photoelectricity, catalysis, electrolysis.
Accompanying drawing explanation
Fig. 1 ~ 3 are that Ti-30Nb alloy is at 10%HNO
3the SEM picture on the ternary oxide film surface after electrolytic solution Anodic Oxidation.
Fig. 4 ~ 7 are that the rear ternary oxide film of Ti-30Nb alloy anode oxidation is through 400 DEG C of heat treated TEM pictures.
Fig. 8 is that Ti-50Nb alloy is at 20%NH
4nO
3the EDS power spectrum of the ternary oxide film after electrolytic solution Anodic Oxidation.
Fig. 9 is that Ti-50Nb alloy is at 20%NH
4nO
3the SEM picture of the ternary oxide film after electrolytic solution Anodic Oxidation.
Figure 10 is that Ti-40Nb alloy ternary oxide film after 5% perchloric acid mixes 5% nitric acid electrolytic solution Anodic Oxidation is schemed through 700 DEG C and 1000 DEG C of heat treated Raman.
Embodiment
Embodiment 1:
Anode selects Ti-30Nb alloy, and negative electrode selects graphite rod, electrolytic solution preparing 10%HNO
3solution.Alloy polished, deoils, ultrasonic, cleaning, after drying, connect two electrode systems, apply voltage 30V, continue 10min, obtain Ti-30Nb-O ternary oxide.Fig. 1 ~ 3 are that Ti-30Nb alloy is at 10%HNO
3the SEM picture of the ternary oxide film after electrolytic solution Anodic Oxidation, as shown in the figure, the surface apertures of ternary oxide is 10 ~ 20nm, aperture, bottom surface is 20 ~ 40nm, pitch of holes 20 ~ 30nm, length-to-diameter ratio are greater than 2000, rate of oxidation is 4g/h, through 60min, 400 DEG C of thermal treatments, in Fig. 4 ~ 7, TEM result shows to obtain anatase octahedrite TiO
2for the ternary oxide film of principal crystalline phase.
Embodiment 2:
Anode selects Ti-50Nb alloy, and negative electrode selects graphite rod, electrolytic solution preparing 20%NH
4nO
3solution.Alloy polished, deoils, ultrasonic, cleaning, after drying, connect two electrode systems, apply voltage 40V, continue 10min, obtain Ti-50Nb-O ternary oxide.In Fig. 8, EDS result shows the composition of ternary oxide, Ti: Nb=1: 1.Fig. 9 is that Ti-50Nb alloy is at 20%NH
4nO
3the SEM picture of the ternary oxide film after electrolytic solution Anodic Oxidation, as shown in the figure, the surface apertures of ternary oxide is 10 ~ 40nm, aperture, bottom surface is 20 ~ 60nm, pitch of holes 20 ~ 30nm, length-to-diameter ratio are greater than 1200, rate of oxidation is 3g/h, through 180min, 700 DEG C of thermal treatments, obtain that there is anatase octahedrite TiO
2with six side phase Nb
2o
5the ternary oxide film of crystalline phase composition.
Embodiment 3:
Anode selects Ti-70Nb alloy, and negative electrode selects graphite rod, and electrolytic solution preparing 5% perchloric acid mixes 5% salpeter solution.Alloy polished, deoils, ultrasonic, cleaning, after drying, connect two electrode systems, apply voltage 60V, continue 10min, obtain Ti-70Nb-O ternary oxide.The surface apertures of ternary oxide is 40 ~ 60nm, aperture, bottom surface is 50 ~ 100nm, pitch of holes 100nm, length-to-diameter ratio is greater than 1000, rate of oxidation is 3g/h, respectively through 60min, 700 DEG C and 60min, 1000 DEG C of thermal treatments, obtain the ternary oxide film with crystalline phase composition.In Figure 10, Raman result obtains anatase octahedrite TiO at showing 700 DEG C
2with six side phase Nb
2o
5the ternary oxide film of composition, and Rutile Type TiO is obtained at 1000 DEG C
2, six side's phases and monoclinic phase Nb
2o
5the ternary oxide film of composition.
Claims (2)
1. a preparation method for ultrafast anode self-assembly bilateral porous nano ternary oxide, is characterized in that comprising the following steps:
1) pre-treatment of Binary Titanium Alloys; Binary Titanium Alloys is carried out spark cutting, then uses the liquid honing of 200#, 400# to surface smoothing; Afterwards at 10 ~ 20g/l NaOH solution, at 80 ~ 100 DEG C, soak 30 ~ 60 min oil removings; Again under ultrasound condition, use acetone and washed with de-ionized water successively, then drying for standby;
2) preparation of electrolytic solution: by oxidizing species and deionized water proportioning in proportion;
3) bilateral porous nano amorphous ternary oxide compound is prepared at alloy surface: adopt two electrode electrolytic pools at normal temperatures, take Binary Titanium Alloys as anode, graphite or platinized platinum are to electrode, under 10 ~ 100V voltage conditions, carry out anodic oxidation 1 ~ 30 min, obtain bilateral porous nano ternary amorphous oxides;
4) Crystallizing treatment: heat-treated by bilateral porous nano ternary amorphous oxides, obtains the bilateral porous nano ternary oxide with certain crystalline phase composition;
In step 1), described alloy is the titanium alloy T i-xNb of uniform ingredients, x is the atomic percentage conc of Nb, and x is 30 ~ 70;
Described oxidizing species is perchloric acid and salt, permanganic acid and salt, nitric acid and salt;
Described oxide surface and bottom surface all in nano-porous structure, surface apertures 10 ~ 60 nm, aperture, bottom surface 20 ~ 100 nm, pitch of holes 10 ~ 150 nm;
Described oxide compound is the oxide film on microcosmic with bilateral, nano-porous structure.
2. preparation method according to claim 1, is characterized in that: step 2) in, in described electrolytic solution, electrolytical concentration of volume percent is 1 ~ 100vol%.
3
.according to claim 1, preparation method, is characterized in that: in step 3), and described oxide compound generating rate is greater than 3g/h.
4
.according to claim 1, preparation method, is characterized in that: in step 4), and described thermal treatment temp is 400 ~ 1000 DEG C, thermal treatment be the time is 30 ~ 180 min.
5
.according to the purposes of bilateral porous nano ternary oxide product described in claim 1, it is characterized in that: described ternary oxide product may be used for photoelectricity, catalysis, water pollutions process, sensor field.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260557A (en) * | 2007-12-10 | 2008-09-10 | 西北有色金属研究院 | Coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof |
| CN101671840A (en) * | 2008-09-10 | 2010-03-17 | 中国科学院金属研究所 | Method for generating nanotube array oxide film on medical titanium and titanium alloy surface |
| CN102071448A (en) * | 2009-11-20 | 2011-05-25 | 莱尔德电子材料(深圳)有限公司 | PVD (Physical Vapor Deposition) and coloring of cold anodic oxidized metal |
| CN102071450A (en) * | 2011-01-19 | 2011-05-25 | 天津大学 | Method for preparing nanostructure oxide film on surface of Ti-25Nb-3Mo-2Sn-3Zr (TLM) titanium alloy |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260557A (en) * | 2007-12-10 | 2008-09-10 | 西北有色金属研究院 | Coaxial double-pipe titanium dioxide nano-pipe array thin film and preparation method thereof |
| CN101671840A (en) * | 2008-09-10 | 2010-03-17 | 中国科学院金属研究所 | Method for generating nanotube array oxide film on medical titanium and titanium alloy surface |
| CN102071448A (en) * | 2009-11-20 | 2011-05-25 | 莱尔德电子材料(深圳)有限公司 | PVD (Physical Vapor Deposition) and coloring of cold anodic oxidized metal |
| CN102071450A (en) * | 2011-01-19 | 2011-05-25 | 天津大学 | Method for preparing nanostructure oxide film on surface of Ti-25Nb-3Mo-2Sn-3Zr (TLM) titanium alloy |
Non-Patent Citations (3)
| Title |
|---|
| 双通TiO2纳米管阵列光催化膜的研制;李广忠 等;《钛工业进展》;20080630;第25卷(第3期);第42-44页 * |
| 阳极氧化法制备二氧化钛纳米管及其在太阳能电池中的应用;李欢欢 等;《物理化学学报》;20110401;第27卷(第5期);第1017-1025页 * |
| 阳极氧化法制备二氧化钛纳米管及其荧光性质;刘素琴等;《无机化学学报》;20070531;第23卷(第5期);第827-832页 * |
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