CN101967654B - Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof - Google Patents
Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof Download PDFInfo
- Publication number
- CN101967654B CN101967654B CN2010105024076A CN201010502407A CN101967654B CN 101967654 B CN101967654 B CN 101967654B CN 2010105024076 A CN2010105024076 A CN 2010105024076A CN 201010502407 A CN201010502407 A CN 201010502407A CN 101967654 B CN101967654 B CN 101967654B
- Authority
- CN
- China
- Prior art keywords
- base material
- titanium base
- carburizing
- titanium
- modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a ruthenium oxide electrode material by adopting carburization and modification of a titanium base material and a preparation method thereof. A Ru oxide active coating is deposited after the titanium base material is carburized and modified. The preparation method of the electrode material comprises the following steps of: carburizing the titanium base material, namely carbonizing at 700-900 DEG C; then coating Ru-contained active slurry on a carburized titanium material; and oxidizing and sintering to form the ruthenium oxide electrode material by adopting carburization and modification of the titanium base material. The obtained electrode material has the electric catalytic activity which is obviously higher than that the conventional electrode material without carburization processing, combines the advantages of a titanium base electrode material and a carbon base electrode material, maintains the mechanical stability of the titanium base electrode material and retains high activity of the carbon base electrode material. The invention only improves the titanium base material, can be suitable for the improvement of the Ru oxide electrode material and has the advantages of simple preparation method, high operability, easy acquisition of raw materials and low cost.
Description
Technical field
The invention belongs to the preparing technical field of the electrode materials of Applied Electrochemistry and energy industry, be specifically related to a kind of adopt titanium base material carburizing modification contain ru oxide electrode materials and preparation method thereof.
Background technology
The electrode materials of electrochemical industry use the earliest is a synthetic graphite.After the oxide compound that contained precious metal element in 1967 comes out, Graphite Electrodes gradually replace by its.It is found that this type oxide has very high electro catalytic activity, therefore be called as the activating oxide material, or simply be called active material.Up to the present, the most superior active material remains and contains the ru oxide material.A large amount of experiments show, adopt the titanium material as carrier, utilize the stability of titanium base material, and what the Ti base of acquisition contained the Ru oxide compound becomes the electrochemical industry high performance electrode material.
Recently, it is base material that people adopt with the carbon material, and deposition contains Ru oxide compound making electrode materials above that, and very common aspect energy electrode materials, its main purpose is exactly to utilize the electroconductibility of carbon material to improve electrode performance.
Summary of the invention
The object of the present invention is to provide a kind of adopt titanium base material carburizing modification contain ru oxide electrode materials and preparation method thereof, thereby can obtain more superior electrocatalysis characteristic.
Employing titanium base material carburizing modification of the present invention contain the ru oxide electrode materials, adopting after the titanium base material carburizing modification again, deposition contains Ru oxide compound activated coating.
Wherein the carburizing modification of titanium base material is the carbonizing treatment through 700～900 ℃, and it is carbon-containing bed to obtain one deck at the titanium substrate surface.Preferably, the carburizing modification of titanium base material is through 800 ℃ carbonizing treatment.
The said Ru of containing oxide compound activated coating is the single Ru of containing oxide compound activated coating or the polynary Ru oxide compound activated coating that contains.The wherein said single Ru of containing oxide compound activated coating is RuO
2Activated coating; The said polynary molar ratio>=10mol% that contains active component Ru in the Ru oxide compound activated coating.
The preparation method of titanium base material carburizing modified electrode material of the present invention comprises titanium base material carburizing pre-treatment, carburizing treatment and follow-up active material deposition, and concrete steps are following:
1) titanium base material pre-treatment:
The titanium base material is through decontamination, and the heating pickling is washed, dried;
2) titanium base material carburizing treatment:
The carburizing treatment that pretreated titanium base material warp is 700～900 ℃, it is carbon-containing bed to obtain one deck at the titanium substrate surface;
3) contain the preparation of Ru active slurry:
The source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h;
4) contain the deposition of Ru activating oxide:
To contain the Ru active slurry and be coated on the titanium base material of carburizing treatment, be heating and curing, oxidation and sinter, the cooling of coming out of the stove; Annealing thermal treatments under 250 ~ 450 ℃ in box-type furnace at last promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
Wherein said titanium base material adopts industrially pure titanium.
For the single oxide activated coating that contains Ru, active component adopts RuCl in the step 3)
3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h; For multicomponent reactive oxide compound activated coating, active component adopts with RuCl
3Be the source material, nonactive constituent element is the source material with other metal-salt, according to the method preparation of conventional multicomponent reactive coating; Method is following: the molar ratio>=10mol% by active component Ru takes by weighing each source material; Be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L; Mix, leave standstill 9 ~ 15h.
Said carburizing treatment adopts solid carburizing, gas cementation or liquid carburizing.Preferred solid carburizing will soon be imbedded in the solid carburizer through pretreated titanium base material, handle through 700～900 ℃ of high temperature cabonizations, and it is carbon-containing bed to obtain one deck at the titanium substrate surface.Preferred 800～850 ℃ of carbonization temperature is more preferably through 800 ℃ carbonizing treatment.
Employing titanium base material carburizing modified electrode material of the present invention and preparation method thereof; Its key is to adopt the titanium base material before the deposition activating oxide; Carry out the carburizing modification earlier and handle, promptly utilize the technology of carburizing, it is carbon-containing bed in titanium base material and activating oxide, to increase one deck; Increasing carbon-containing bed purpose is that the electroconductibility in active coating and the titanium base material is increased, thereby improves the performance of electrode.
Titanium base material carburizing modification provided by the invention contains the Ru oxide electrode material; Had the advantage of titanium-matrix electrode material and carbon-based electrode material concurrently; The mechanical stability that had both kept the titanium-matrix electrode material has also kept the high reactivity of carbon-based electrode material, for electrode materials provides a kind of plan.
Titanium base of the present invention carburizing contains the Ru oxide material, has than existing titanium base to contain the much higher electro catalytic activity of Ru oxide material.Can be applied to electrochemistry parts and devices such as aqueous electrolysis, electrochemical capacitance, organic solution electrolysis, fuel cell.The present invention only improves the titanium base material, goes for containing the improvement of Ru oxide electrode material, and the preparation method is simple, and is workable, and raw material is easy to get, and cost is low.
Remarkable advantage of the present invention:
A) the invention solves employing is the mechanical stability of substrate preparation high reactivity electrode materials with the carbon material, suitable especially preparation film-type and small-sized electrode materials.Not only can obtain to have the high reactivity that carbon back contains Ru activating oxide material through technology of the present invention, can also solve the difficult problem that carbon back contains the easy fracture of ruthenium activating oxide material and is difficult to the manufacturing small-sized device.
B) adopt material of the present invention and preparation technology can further improve the electro catalytic activity that conventional titanium base contains the Ru oxide material.The activity that contains the Ru activating oxide for different sorts promotes and can play a significant role.
C) carburizing treatment that adopts of the present invention is easy to get at the raw material raw material, technology is simple, can realize scale operation.The high activity oxide material that obtains, cost is very low, and technology is simple, feasible, has reached practicability and industrialized condition.
Description of drawings
Fig. 1 is the cyclic voltammetry curve of two kinds of electrodes; Wherein 1 is traditional titanium coated Ru
0.3Ti
0.7O
2Anode, 2 titaniums for 800 ℃ of carburizings of warp employing are the Ru that base material is covered again
0.3Ti
0.7O
2Anode.
Embodiment
Employing titanium base material carburizing modified electrode material of the present invention and preparation method thereof relates generally to carburization process and thermal decomposed deposition method.Concrete implementation step is following:
1) titanium base material treatment:
The titanium base material mainly adopts the industrially pure titanium material.Base material is through heating degrease in containing the washing powder of 100g/L, the heating pickling is 1 hour in the oxalic acid solution of 50g/L, washing and oven dry.
2) solid carburizing of titanium base material is handled:
Conventional solid carburizing method is adopted in the carburizing of titanium base material.Be about to titanium and case through pretreated titanium base material, imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, and carbonizing treatment is 1 hour under through 700～900 ℃ temperature, and is carbon-containing bed at titanium substrate surface acquisition one deck.The carburizing of titanium base material can be adopted methods such as solid carburizing, gas cementation and liquid carburizing.
3) contain the preparation of Ru active slurry: for the single oxide activated coating that contains Ru, active component adopts with RuCl
3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry mixes being 0.5 ~ 5 mol/L, leaves standstill 9 ~ 15h;
For multicomponent reactive oxide compound activated coating, active component adopts with RuCl
3Be the source material; Nonactive constituent element can other metal-salt be the source material according to routine; Comprise that in titanium chloride, tin chloride, NSC 51149, the Cerium II Chloride etc. one or more are (referring to Zhang Teng " the high cerium of nano level contains phase structure, thermodynamics, kinetics and the chemical property of ruthenium activating oxide "; University of Fuzhou's Ph D dissertation, 2009).According to the method preparation of conventional multicomponent reactive coating, method is following: take by weighing each source material, wherein molar ratio >=10mol% of active component Ru; Be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L; Mix, leave standstill 9 ~ 15h.
4) contain the deposition of Ru activating oxide:
To contain the layering of Ru active slurry is coated on the carburizing titanium material; Through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ be heating and curing after, oxidation and sinter 10min in 250 ~ 450 ℃ box-type furnace; The cooling of coming out of the stove, at last in box-type furnace 250 ~ 450 ℃ of annealing thermal treatments down.Promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
The constructional feature of the titanium base material carburizing modified electrode material that obtains through above-mentioned enforcement of the present invention is that increase one deck is carbon-containing bed in titanium base material and activating oxide; The carbon-containing bed purpose that increases is that the electroconductibility in active coating and the titanium base material is increased, thereby improves the performance of electrode.
The performance characteristics of the titanium base material carburizing modified electrode material that obtains through above-mentioned enforcement of the present invention is to have very high electro catalytic activity.For example we are with the experiment that compares of acquisition titanium base material carburizing modified electrode material and unmodified titanium-matrix electrode material, and the result shows that the activity of the electrode materials that is obtained is significantly increased.Because the size of the integral charge area of cyclic voltammetry curve has determined the activity of electrode materials.Its raising embodies a concentrated reflection of in the increase of integral charge Q* of cyclic voltammetry curve, and as shown in Figure 1, test condition is :-0.1-1.1V potential range, carry out the cyclic voltammetric test with the scanning speed of 25mv/s, and electrolytic solution is 0.5mol/L H
2SO
4Solution.That mark 1 is traditional Ru among the figure
0.3Ti
0.7O
2The cyclic voltammetry curve of the anode material of mixed oxide.The encirclement area of its cyclic voltammetry curve is less, and the integral charge Q* of cyclic voltammetry curve is less, so its electro catalytic activity is not outstanding.And the curve of the mark 2 shown in Fig. 1 is for through the titanium of 800 ℃ of carburizings being the base material Ru that is covered again
0.3Ti
0.7O
2The cyclic voltammetry curve of the anode material of mixed oxide.Can find out that the area that its cyclic voltammetry curve surrounded is very big, increase about 1.5 times than the corresponding integral charge that does not carry out the electrode materials of carbonizing treatment.Explain that the present invention has tangible effect to the electrocatalysis characteristic that improves electrode materials.Also clearly illustrated that this improvement effect with the experiment on year-on-year basis of traditional anode material.
Below be several practical implementation example of the present invention, but the present invention not only is limited to this.
Embodiment 1
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, through carbonizing treatment under 900 ℃ the temperature 1 hour, obtains the titanium plate of handling through carbonizing and modifying.
Reactive coating is the source material with the ruthenium trichloride, is dissolved in ethanolic soln, mixes.The concentration of solute is controlled at 1.5 mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations; Again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove; Continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface; The cooling of coming out of the stove is the electrode materials of titanium base material carburizing modification.Prepare the electrode materials without carbonizing treatment simultaneously, their other experiment condition is identical.Adopt electrochemical workstation to compare and measure and show that through the electrode materials after the carbonizing treatment, the integral charge Q* of its cyclic voltammetry curve has increased about 1.3 times.
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, through carbonizing treatment under 850 ℃ the temperature 1 hour, obtains the titanium plate of handling through carbonizing and modifying.
Reactive coating is with ruthenium trichloride and TiCl
3Being the source material, is that the ratio of 3:7 is dissolved in ethanolic soln in the mole number of Ru:Ti, mixes.The concentration of solute is controlled at 0.5 mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations; Again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove; Continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface; The cooling of coming out of the stove is the Ru that is covered after the titanium base material carburizing modification
0.3Ti
0.7O
2The electrode materials of mixed oxide.Prepare electrode materials simultaneously, promptly traditional Ru without carbonizing treatment
0.3Ti
0.7O
2The anode material of mixed oxide.Adopt electrochemical workstation to compare mensuration to the two and show, through the lining Ru after the carbonizing treatment
0.3Ti
0.7O
2Electrode materials, the integral charge Q* of its cyclic voltammetry curve is than traditional lining Ru
0.3Ti
0.7O
2Electrode materials increased about 1.5 times.
Embodiment 3
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, through carbonizing treatment under 750 ℃ the temperature 1 hour, obtains the titanium plate of handling through carbonizing and modifying.
Reactive coating is with ruthenium trichloride, SnCl
4And TiCl
3Being the source material, is that the ratio of 3:0.5:6.5 is dissolved in ethanolic soln in the mole number of Ru:Sn:Ti, mixes.The concentration of solute is controlled at 5mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations; Again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove; Continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface; The cooling of coming out of the stove is the Ru that is covered after the titanium base material carburizing modification
0.30Sn
0.05Ti
0.0.65O
2The electrode materials of mixed oxide.Prepare electrode materials simultaneously, promptly traditional Ru without carbonizing treatment
0.30Sn
0.05Ti
0.0.65O
2The anode material of mixed oxide.Adopt electrochemical workstation to compare mensuration to the two and show, through the lining Ru after the carbonizing treatment
0.30Sn
0.05Ti
0.0.65O
2Electrode materials, the integral charge Q* of its cyclic voltammetry curve is than traditional lining Ru
0.30Sn
0.05Ti
0.0.65O
2Electrode materials increased about 1.2 times.
Claims (8)
- One kind adopt titanium base material carburizing modification contain the ru oxide electrode materials, it is characterized in that: adopting after the titanium base material carburizing modification again, deposition contains Ru oxide compound activated coating; The carburizing modification of titanium base material is that titanium is cased through pretreated titanium base material, and imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, and again through carbonizing treatment under 700～900 ℃ the temperature 1 hour, it is carbon-containing bed to obtain one deck at the titanium substrate surface.
- 2. employing titanium base material carburizing modification according to claim 1 contain the ru oxide electrode materials, it is characterized in that: the carburizing modification of said titanium base material is the carbonizing treatment through 800 ℃.
- 3. employing titanium base material carburizing modification according to claim 1 contain the ru oxide electrode materials, it is characterized in that: the said Ru of containing oxide compound activated coating is the single Ru of containing oxide compound activated coating or the polynary Ru of containing oxide compound activated coating.
- 4. employing titanium base material carburizing modification according to claim 3 contain the ru oxide electrode materials, it is characterized in that: the said single Ru of containing oxide compound activated coating is RuO 2Activated coating.
- 5. employing titanium base material carburizing modification according to claim 3 contain the ru oxide electrode materials, it is characterized in that: molar ratio >=10mol% of active component Ru in the said polynary Ru of the containing oxide compound activated coating.
- 6. the preparation method who contains the ru oxide electrode materials of an employing titanium base material carburizing modification as claimed in claim 1, it is characterized in that: said preparing method's concrete steps are following:1) titanium base material pre-treatment:The titanium base material is through decontamination, and the heating pickling is washed, dried;2) titanium base material carburizing treatment:Conventional solid carburizing method is adopted in the carburizing of titanium base material; Be about to titanium and case through pretreated titanium base material, imbedding carbonated barium and graphite mass ratio is in the solid carburizer of 90:10, through carbonizing treatment under 700～900 ℃ the temperature 1 hour, carbon-containing bed at titanium substrate surface acquisition one deck again;3) contain the preparation of Ru active slurry:The source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h;4) contain the deposition of Ru activating oxide:To contain the Ru active slurry and be coated on the titanium base material of carburizing treatment, be heating and curing, oxidation and sinter, the cooling of coming out of the stove; Annealing thermal treatments under 250 ~ 450 ℃ in box-type furnace at last promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
- 7. employing titanium base material carburizing modification according to claim 6 contain ru oxide electrode materials preparation method, it is characterized in that: said titanium base material adopts industrially pure titanium.
- 8. employing titanium base material carburizing modification according to claim 6 contain ru oxide electrode materials preparation method, it is characterized in that: for the single oxide activated coating that contains Ru, active component adopts RuCl in the step 3) 3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h; For multicomponent reactive oxide compound activated coating, active component adopts with RuCl 3Be the source material, nonactive constituent element is the source material with other metal-salt, according to the method preparation of conventional multicomponent reactive coating; Method is following: the molar ratio>=10mol% by active component Ru takes by weighing each source material; Be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L; Mix, leave standstill 9 ~ 15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105024076A CN101967654B (en) | 2010-10-11 | 2010-10-11 | Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105024076A CN101967654B (en) | 2010-10-11 | 2010-10-11 | Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101967654A CN101967654A (en) | 2011-02-09 |
| CN101967654B true CN101967654B (en) | 2012-06-27 |
Family
ID=43546872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105024076A Expired - Fee Related CN101967654B (en) | 2010-10-11 | 2010-10-11 | Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101967654B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017113382A1 (en) * | 2015-12-31 | 2017-07-06 | 深圳凯世光研股份有限公司 | Carburising treatment process for thorium-tungsten electrode |
| CN110158087B (en) * | 2019-05-16 | 2020-05-22 | 西安交通大学 | Preparation method of laminated electrolytic oxidation water electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3788968A (en) * | 1971-01-08 | 1974-01-29 | Metallgesellschaft Ag | Layered electrode |
| CN1612949A (en) * | 2002-01-03 | 2005-05-04 | 拜尔材料科学股份公司 | Electrode for electrolysis in acidic media |
| CN101289750A (en) * | 2008-06-13 | 2008-10-22 | 福州大学 | Titanium anodic of nano TiO2 seed coating and method for preparing same |
-
2010
- 2010-10-11 CN CN2010105024076A patent/CN101967654B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3788968A (en) * | 1971-01-08 | 1974-01-29 | Metallgesellschaft Ag | Layered electrode |
| CN1612949A (en) * | 2002-01-03 | 2005-05-04 | 拜尔材料科学股份公司 | Electrode for electrolysis in acidic media |
| CN101289750A (en) * | 2008-06-13 | 2008-10-22 | 福州大学 | Titanium anodic of nano TiO2 seed coating and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101967654A (en) | 2011-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Subban et al. | Sol− gel synthesis, electrochemical characterization, and stability testing of Ti0. 7W0. 3O2 nanoparticles for catalyst support applications in proton-exchange membrane fuel cells | |
| Huang et al. | Synthesis of high-performance titanium sub-oxides for electrochemical applications using combination of sol–gel and vacuum-carbothermic processes | |
| Maeda et al. | Calcium niobate nanosheets prepared by the polymerized complex method as catalytic materials for photochemical hydrogen evolution | |
| CN109518168B (en) | Preparation method of active titanium-based electrode plate with high-stability coating | |
| Duan et al. | Enhanced electrocatalytic activity of nano-TiN composited Ti/Sb–SnO 2 electrode fabricated by pulse electrodeposition for methylene blue decolorization | |
| Song et al. | Influence of Nd-doping on the degradation performance of Ti/Sb-SnO2 electrode | |
| JP2014521828A (en) | Electrochemical electrode and method for producing the same | |
| Bi et al. | Preparation and performance of highly active and long-life mesopore Ti/SnO2–Sb electrodes for electrochemical degradation of phenol | |
| Dong et al. | Theoretical calculation and experimental study on the conductivity and stability of Bi-doped SnO2 electrode | |
| CN101967654B (en) | Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof | |
| Yan et al. | Promotion of in situ TiNx interlayer on morphology and electrochemical properties of titanium based IrO2-Ta2O5 coated anode | |
| CN106400045B (en) | A kind of titanium phosphor codoping iron oxide photoelectrode and preparation method thereof | |
| Matsumoto et al. | A new preparation method of barium titanate perovskite film using electrochemical reduction | |
| CN1995463A (en) | Electrochemical industrial titanium anode with oxide seed layer | |
| Chu et al. | Fabrication and structural characteristics of ordered TiO2− Ru (− RuO2) nanorods in porous anodic alumina films on ITO/glass substrate | |
| CN101372751B (en) | Nano SnO2 seed embedded coating titanium anode and preparation thereof | |
| CN103774175A (en) | Ruthenium zirconium tin titanium oxide-embedded active coating and preparation method thereof | |
| Takasu et al. | Ti‐V‐W‐O/Ti Oxide Electrodes as Candidates for Electrochemical Capacitors | |
| CN106967979A (en) | A kind of phosphoric acid cobalt catalyst is modified BiFeO3Film photoelectric electrode and preparation method thereof | |
| Rezaee et al. | Electrochemical and Oxidation Behavior of Yttria Stabilized Zirconia Coating on Zircaloy‐4 Synthesized via Sol‐Gel Process | |
| Yao et al. | Active Ti/SnO2 anodes for pollutants oxidation prepared using chemical vapor deposition | |
| EP0545869B1 (en) | Electrolytic electrode | |
| CN103898589A (en) | Preparation method of nanometer bismuth oxide film | |
| CN103305866A (en) | Preparation method of iridium oxide nanometer coating electrode taking aluminum oxide-based composite material as base body | |
| CN104099636A (en) | Method for preparing metal oxide electrode by powder curing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120627 Termination date: 20201011 |