CN103255457B - A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium - Google Patents
A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium Download PDFInfo
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- CN103255457B CN103255457B CN201310157167.4A CN201310157167A CN103255457B CN 103255457 B CN103255457 B CN 103255457B CN 201310157167 A CN201310157167 A CN 201310157167A CN 103255457 B CN103255457 B CN 103255457B
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Abstract
A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium, is applied to photo-electrocatalytic technology field.What at present report was maximum is the TiO 2 nanotubes modified electrode of noble metal platinum, there is electric current density low, poisoning seriously, the shortcoming that catalytic performance is not high.The TiO 2 nanotubes modified electrode of nano platinum/ruthenium prepared by the present invention, in titanium sheet, the Nano tube array of titanium dioxide that arrangement is regular, vertical orientated is prepared initially with anodizing, then the method adopting pulse electrodeposition, prepares the TiO 2 nanotubes modified electrode of nano platinum/ruthenium.The synergism of platinum and ruthenium can eliminate the CO being adsorbed on precious metal surface, reduces the toxic of catalyst, and meanwhile, catalysis take-off potential is significantly negative to be moved, and the electrocatalysis characteristic of electrode is improved, and has important researching value and is widely applied prospect.
Description
Technical field
A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nano platinum/ruthenium, belongs to photo-electrocatalytic technology field.
Background technology
TiO2Nano-tube array produces skin effect, quantum size effect etc. due to its special construction, there is the features such as specific surface area is big, stability is high, acid-fast alkali-proof is strong, PhotoelectrocatalytiPerformance Performance is good, it is the optimal electrode material of catalyst carrier, in photoelectrocatalysis field, there is very wide application prospect.By the catalysis high noble metal nano microgranule of activity and TiO2Nanotube combines, it is possible to obtains the novel electrode of catalysis activity height, stable performance, has caused extensive attention.
What research was more at present is the TiO 2 nanotubes modified electrode of Platinum Nanoparticles, there is the shortcoming that electric current density is low, poisoning seriously, catalytic performance is not high.Have been reported the synergism pointing out platinum and ruthenium and can significantly improve the CO tolerance catalysts of electrode, make the negative shifting of catalysis take-off potential, make fuel cell catalytic performance when containing CO fuel handling be significantly improved than use Pt catalyst.And, the relative Pt of noble metal Ru, cost is only about 1/5, can greatly reduce electrode cost, be advantageously implemented the requirement of its industrialization.
The method being generally adopted unidirectional current chemical deposition at present deposits nano-noble metal granule on titania nanotube, and the deficiency of this method is that electric current density is very low, liberation of hydrogen and concentration polarization is serious, deposition layer is uneven.Pulse electrodeposition can use very big pulse current density when particularly pulse ON time is Millisecond, metal ion is deposited under high overpotential, it is possible not only to reduce nanoparticle size, increases specific surface area, it is also possible to the ratio shared by side reaction such as reduction liberation of hydrogen.And increase cathode activation polarization also can reduce the concentration polarization of electrolyte.There is with this TiO 2 nanotubes modified electrode of prepared nano platinum/ruthenium the electrocatalysis characteristic of excellence, and stability is high, poisoning alleviate, have a great economic significance.
Summary of the invention
Problem to be solved by this invention is to provide a kind of pulse electrodeposition and prepares the new technique of the TiO 2 nanotubes modified electrode of nano platinum/ruthenium, prepares Pt/Ru-TiO of good performance with the technique of the method for pulse electrodeposition and simple and stable2/ Ti nanotube electrode, the difficult problem that when overcoming direct current deposition, electric current density is low and evolving hydrogen reaction is serious.The present invention is possible not only to increase substantially the CO tolerance catalysts of electrode, makes catalysis take-off potential significantly bear and moves, and stable performance, electro catalytic activity significantly improves.
The preparation process of the present invention comprises the following steps:
1), after titanium sheet being polished on sand paper, ultrasonic cleaning is carried out with acetone, ethanol and deionized water respectively, to remove surface and oil contaminant, then clean with distilled water flushing, after drying as electrode basement；
2) constant voltage DC anodizing is adopted to prepare titania nanotube.With titanium sheet for anode, graphite is negative electrode, and electrolyte is containing 1～5g/LNH4HF2With 50～200g/LH2The ethylene glycol solution of O, temperature controls at 10～30 DEG C, and voltage is set to 10～60V, and the time is 1～6h, and period adopts magnetic agitation；
3) TiO prepared2Nanotube carries out heat treatment at 350～500 DEG C, and the time is 1～4h, furnace cooling.
4) with TiO2Nanotube is working electrode, pure platinum electrode is to electrode, immersing in the electrolyte that platinum, ruthenium molar concentration rate are 4:1～1:4 and carry out pulse electrodeposition, impulse waveform is: cathodic pulse current density is-350～-50mA/cm, pulse anode current density is 50～350mA/cm2, negative electrode, anodic pulse ON time are 1～6ms, turn-off time 1s, and electrodeposition time is 5～25min, and temperature is room temperature, and deposition process adopts magnetic agitation；
5) after deposition terminates, with distilled water flushing, dry up, prepare the TiO 2 nanotubes modified electrode of nano platinum/ruthenium.
The deposited electrolyte that above-mentioned steps (4) is prepared is for containing 1.0～4.0mM chloroplatinic acid, 0.5～10mM ruthenium trichloride and 0.5M sulfur aqueous acid.
The invention has the beneficial effects as follows:
The synergism of platinum and ruthenium can eliminate the CO being adsorbed on precious metal surface, reduces the toxic of catalyst, and meanwhile, catalysis take-off potential is significantly negative to be moved, and the electrocatalysis characteristic of electrode is improved, and has important researching value and is widely applied prospect.Owing to have employed impulse electrodeposition technology, relative to the electrode that general DC electrodeposition prepares, not only can reduce sedimentation time, the make consumption of noble metal also can be greatly lowered, reduce cost.The TiO 2 nanotubes modified electrode of nano platinum/ruthenium prepared by the present invention, compared with the TiO 2 nanotubes modified electrode of single Platinum Nanoparticles, has higher electro catalytic activity and CO tolerance catalysts, is with a wide range of applications in photoelectrocatalysis field.
Accompanying drawing explanation
Fig. 1: the impulse waveform schematic diagram in electrodeposition process.
Fig. 2: specific embodiment 1 prepares the catalysis methanol CV curve of electrode.
Fig. 3: specific embodiment 2 prepares the catalysis methanol CV curve of electrode.
Fig. 4: specific embodiment 3 prepares the catalysis methanol CV curve of electrode.
Fig. 5: specific embodiment 4 prepares the catalysis methanol CV curve of electrode.
Fig. 6: specific embodiment 2 prepares the surface SEM shape appearance figure of electrode.
Fig. 7: specific embodiment 2 prepares the energy spectrogram of electrode.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following example.In order to make test data have comparability, so variant catalyst is circulated volt-ampere test under identical testing conditions, namely test condition unification is:
To electrode: platinum electrode；
Reference electrode: saturated calomel electrode；
Electrolyte: 0.5MH2SO4+1MCH3The solution of OH
Potential scan rate=50mV/s；
Example 1, the TA1 titanium plate surface of 1cm*1cm is processed after, (after surface treatment polish by titanium sheet on sand paper, remove surface and oil contaminant with acetone ultrasonic cleaning, place into ultrasonic cleaning in ethanol, then with distilled water flushing totally, make electrode after drying.Following example is all identical) put into containing 1g/LNH4HF2、50g/LH2The ethylene glycol solution of O, carries out anodic oxidation 1h at constant voltage 60V, temperature 10 DEG C, period continuous mechanical agitation.The TiO prepared2Nanotube carries out heat treatment at 500 DEG C, and the time is 2h, furnace cooling.TiO after high-temperature heat treatment2Nanotube is put in the mixed aqueous solution containing 4.0mM chloroplatinic acid, 4.0mM ruthenium trichloride and 0.5M sulphuric acid, negative electrode, pulse anode current density respectively-250mA/cm, 250mA/cm2, cathode pulse ON time is 6ms, anodic pulse ON time 1ms, turn-off time 1s, and electrodeposition time is 15min, namely prepares working electrode electrode.Adopt cyclic voltammetry to carry out the electrocatalytic oxidation of methanol in three electrode test systems, record CV curve such as Fig. 2.
Example 2, the TA1 titanium plate surface of 1cm*1cm is processed after, (after surface treatment polish by titanium sheet on sand paper, remove surface and oil contaminant with acetone ultrasonic cleaning, place into ultrasonic cleaning in ethanol, then with distilled water flushing totally, make electrode after drying.Following example is all identical) put into containing 3g/LNH4HF2、100g/LH2The ethylene glycol solution of O, carries out anodic oxidation 4h at constant voltage 30V, temperature 20 DEG C, period continuous mechanical agitation.The TiO prepared2Nanotube carries out heat treatment at 450 DEG C, and the time is 4h, furnace cooling.TiO after high-temperature heat treatment2Nanotube put into containing 4.0mM chloroplatinic acid, 1.0mM ruthenium trichloride, 0.5M sulphuric acid mixed aqueous solution in, negative electrode, pulse anode current density respectively-350mA/cm, 350mA/cm2, negative electrode, anodic pulse ON time are 2ms, turn-off time 1s, and electrodeposition time is 10min, namely prepare working electrode electrode.Adopt cyclic voltammetry to carry out the electrocatalytic oxidation of methanol in three electrode test systems, record CV curve such as Fig. 3.
Example 3, the TA1 titanium plate surface of 1cm*1cm is processed after, (after surface treatment polish by titanium sheet on sand paper, remove surface and oil contaminant with acetone ultrasonic cleaning, place into ultrasonic cleaning in ethanol, then with distilled water flushing totally, make electrode after drying.Following example is all identical) put into containing 5g/LNH4HF2、200g/LH2The ethylene glycol solution of O, carries out anodic oxidation 6h at constant voltage 10V, temperature 30 DEG C, period continuous mechanical agitation.The TiO prepared2Nanotube carries out heat treatment at 350 DEG C, and the time is 4h, furnace cooling.TiO after high-temperature heat treatment2Nanotube put into containing 1.0mM chloroplatinic acid, 0.5mM ruthenium trichloride, 0.5M sulphuric acid mixed aqueous solution in, negative electrode, pulse anode current density respectively-350mA/cm, 350mA/cm2, negative electrode, anodic pulse ON time are 1ms, turn-off time 1s, and electrodeposition time is 25min, namely prepare working electrode.Adopt cyclic voltammetry to carry out the electrocatalytic oxidation of methanol in three electrode test systems, record CV curve such as Fig. 4.
Example 4, the TA1 titanium plate surface of 1cm*1cm is processed after, (after surface treatment polish by titanium sheet on sand paper, remove surface and oil contaminant with acetone ultrasonic cleaning, place into ultrasonic cleaning in ethanol, then with distilled water flushing totally, make electrode after drying.Following example is all identical) put into containing 3g/LNH4HF2、50g/LH2The ethylene glycol solution of O, carries out anodic oxidation 2h at constant voltage 40V, temperature 20 DEG C, period continuous mechanical agitation.The TiO prepared2Nanotube carries out heat treatment at 400 DEG C, and the time is 3h, furnace cooling.Put into containing 4.0mM chloroplatinic acid, 10mM ruthenium trichloride, 0.5M sulphuric acid mixed aqueous solution in, negative electrode, pulse anode current density respectively-50mA/cm, 50mA/cm2, cathode pulse ON time is 2ms, anodic pulse ON time 4ms, turn-off time 1s, and electrodeposition time is 5min, namely prepares working electrode electrode.Adopt cyclic voltammetry to carry out the electrocatalytic oxidation of methanol in three electrode test systems, record CV curve such as Fig. 5.
The pulse electrodeposition parameter of the different preparation condition (embodiment 1-4) of table 1
The performance parameter of table 2 Different electrodes (embodiment 1-4) catalysis methanol
Claims (1)
1. the method that a pulse electrodeposition prepares the TiO 2 nanotubes modified electrode of nano platinum/ruthenium, it is characterised in that preparation process comprises the following steps:
1) after titanium sheet being polished on sand paper, remove surface and oil contaminant with acetone ultrasonic cleaning, place into ultrasonic cleaning in ethanol, then clean with distilled water flushing, after drying as electrode basement；
2) constant voltage DC anodizing is adopted to prepare titania nanotube.With titanium sheet for anode, graphite is negative electrode, and electrolyte is containing 1～5g/LNH4HF2, 50～200g/LH2The ethylene glycol solution of O, temperature controls at 10～30 DEG C, and voltage is set to 10～60V, and the time is 1～6h, and period adopts magnetic agitation；
3) TiO prepared2Nanotube carries out heat treatment at 350～500 DEG C, and the time is 1～4h, furnace cooling；
4) with TiO2Nanotube is working electrode, and pure platinum electrode is to electrode, immerse platinum, ruthenium molar concentration rate be 4:1～1:4 electrolyte in carry out pulse electrodeposition, impulse waveform is: cathodic pulse current density is-350～-50mA/cm2, pulse anode current density be 50～350mA/cm2, negative electrode, anodic pulse ON time are 1～6ms, turn-off time 1s, and electrodeposition time is 5～25min, and temperature is room temperature, and deposition process adopts magnetic agitation；
5) after deposition terminates, with distilled water flushing, dry up, prepare the TiO 2 nanotubes modified electrode of nano platinum/ruthenium；
Step 4) deposited electrolyte prepared be containing 1.0～4.0mM chloroplatinic acid, 0.5～10mM ruthenium trichloride, 0.5M sulphuric acid mixed aqueous solution.
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| CN104694991A (en) * | 2014-12-30 | 2015-06-10 | 云南大学 | Method for preparing platinum-gold double metal doped TiO2 nanotube electrode |
| CN106637334B (en) * | 2016-09-26 | 2018-09-18 | 首都师范大学 | A kind of method and products thereof of impurity element ratio and chemical property in controlling valve metal-anodicoxide film |
| CN107012494B (en) * | 2017-03-16 | 2019-04-26 | 东北大学 | One-step method is prepared using metal or alloy as the method for the metal oxide supported nanocatalyst of matrix |
| KR102250649B1 (en) * | 2019-11-07 | 2021-05-12 | 한국과학기술연구원 | Method for modifying electrochemical electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054683A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry |
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| CN101560669A (en) * | 2009-04-24 | 2009-10-21 | 同济大学 | Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
| CN102703942A (en) * | 2012-06-20 | 2012-10-03 | 北京工业大学 | Method for preparing nano-platinum/palladium titanium dioxide nanotube composite electrode by pulse electrodeposition |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054683A (en) * | 2007-02-09 | 2007-10-17 | 上海大学 | Method of preparing anode catalysis electrode for preparing hydrogen by electrolyzing coal slurry |
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| CN101560669A (en) * | 2009-04-24 | 2009-10-21 | 同济大学 | Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
| CN102703942A (en) * | 2012-06-20 | 2012-10-03 | 北京工业大学 | Method for preparing nano-platinum/palladium titanium dioxide nanotube composite electrode by pulse electrodeposition |
Non-Patent Citations (2)
| Title |
|---|
| Pt-Ru 合金薄膜的电沉积制备及其电化学表面增强红外吸收光谱;李巧霞等;《物理化学学报》;20100630;第26卷(第6期);第1488-1492页 * |
| 直接甲醇燃料电池用抗CO 电催化剂研究进展;蔡杭锋等;《浙江工业大学学报》;20070630;第35卷(第3期);第255-261页 * |
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