CN103255457A - Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition - Google Patents
Method for preparing nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition Download PDFInfo
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- CN103255457A CN103255457A CN2013101571674A CN201310157167A CN103255457A CN 103255457 A CN103255457 A CN 103255457A CN 2013101571674 A CN2013101571674 A CN 2013101571674A CN 201310157167 A CN201310157167 A CN 201310157167A CN 103255457 A CN103255457 A CN 103255457A
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Abstract
The invention discloses a method for preparing a nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition, and is applied to the technical field of photoelectrocatalysis. At present, most of the defects of a precious metal platinum modified titanium dioxide nanotube electrode include low current density, severe poisoning and low catalytic performance. The method for preparing the nano platinum/ruthenium modified titanium dioxide nanotube electrode provided by the invention comprises the following steps of: firstly preparing titanium dioxide nanotube arrays which are ranked in order and are oriented vertically on a titanium sheet by adopting an anodic oxidation method, and then preparing the nano platinum/ruthenium modified titanium dioxide nanotube electrode by adopting a pulse electrodeposition method. CO adsorbed on the surface of precious metal can be eliminated by the synergistic effect of platinum and ruthenium; catalyst damage is lowered; meanwhile, the catalytic initial potential moves negatively obviously, and the electro-catalytic property of the electrode is improved; and the method for preparing the nano platinum/ruthenium modified titanium dioxide nanotube electrode by utilizing pulse electrodeposition has an important research value and wide application prospects.
Description
Technical field
A kind of pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium, belongs to the photoelectrocatalysis technical field.
Background technology
TiO
2Nano-tube array is owing to its special construction produces surface effects, quantum size effect etc., have characteristics such as specific surface area is big, stability is high, acid-fast alkali-proof is strong, the photoelectrocatalysis performance is good, be the optimal electrode materials of support of the catalyst, have very wide application prospect in the photoelectrocatalysis field.Noble metal nano particulate and TiO that catalytic activity is high
2Nanotube combines, and can access the novel electrode of catalytic activity height, stable performance, has caused extensive attention.
What research was more at present is the TiO 2 nanotubes modified electrode of nanometer platinum, has low, the shortcoming serious, that catalytic performance is not high of poisoning of current density.Existing report points out that the synergy of platinum and ruthenium can significantly improve the anti-CO toxic of electrode, the catalysis take-off potential is born moved, and makes the catalytic performance of fuel cell when containing the CO fuel handling and is significantly improved than using the Pt catalyzer.And the relative Pt of precious metal Ru, cost only are about 1/5, can greatly reduce the electrode cost, are conducive to realize the requirement of its industrialization.
The present general method depositing nano noble metal granule on titania nanotube that adopts the direct current electroless plating, the deficiency of this method are that current density is very low, liberation of hydrogen and concentration polarization is serious, settled layer is inhomogeneous.Pulse electrodeposition can use very large pulse current density when particularly the pulse ON time is Millisecond, make metal ion in high overpotential deposit, not only can reduce nanoparticle size, increase specific surface area, can also reduce the shared ratios of side reaction such as liberation of hydrogen.And increase the concentration polarization that the activation of cathode polarization also can reduce electrolytic solution.Make the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium with this and have excellent electrocatalysis characteristic, and stability is high, poisoning alleviates, and has a great economic significance.
Summary of the invention
Problem to be solved by this invention provides the new technology that a kind of pulse electrodeposition prepares the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium, makes well behaved Pt/Ru-TiO with the method for pulse electrodeposition and the technology of simple and stable
2/ Ti nanotube electrode, the low and serious difficult problem of evolving hydrogen reaction of current density when overcoming the direct current deposition.The present invention not only can increase substantially the anti-CO toxic of electrode, makes significantly negative moving of catalysis take-off potential, and stable performance, and electro catalytic activity obviously improves.
Preparation process of the present invention may further comprise the steps:
1) with the titanium sheet after sand paper polishing, carry out ultrasonic cleaning with acetone, alcohol and deionized water respectively, clean with distilled water flushing then to remove surface and oil contaminant, dry afterwards as electrode basement;
2) adopt constant voltage dc anodizing legal system to be equipped with titania nanotube.Be anode with the titanium sheet, graphite is negative electrode, and electrolytic solution is for containing 1～5g/L NH
4HF
2With 50～200g/L H
2The ethylene glycol solution of O, temperature is controlled at 10～30 ℃, voltage is set to 10～60V, the time is 1～6h, during adopt magnetic agitation;
3) TiO that makes
2Nanotube is heat-treated under 350～500 ℃, and the time is 1～4h, furnace cooling.
4) with TiO
2Nanotube is working electrode, pure platinum electrode is counter electrode, immerse platinum, ruthenium molar concentration rate and be in the electrolytic solution of 4:1～1:4 and carry out pulse electrodeposition, pulse waveform is: pulse cathode current density is-350～-50mA/cm, pulse anode current density are 50～350mA/cm
2, negative electrode, anodic pulse ON time are 1～6ms, and turn-off time 1s, electrodeposition time are 5～25min, and temperature is room temperature, and deposition process adopts magnetic agitation;
5) after deposition finishes, with distilled water flushing, dry up, make the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium.
The deposited electrolyte that above-mentioned steps (4) is prepared is the aqueous solution that contains 1.0～4.0mM Platinic chloride, 0.5～10mM ruthenium trichloride and 0.5M sulfuric acid.
The invention has the beneficial effects as follows:
The synergy of platinum and ruthenium can be eliminated the CO that is adsorbed on precious metal surface, reduces the toxic of catalyzer, and simultaneously, the catalysis take-off potential is negative moving significantly, and the electrocatalysis characteristic of electrode is improved, and has important researching value and application prospect widely.Owing to adopted impulse electrodeposition technology, the electrode with respect to general dc electrodeposition makes not only can reduce depositing time, also can reduce the usage quantity of precious metal significantly, reduces cost.The TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium of the present invention's preparation is compared with the TiO 2 nanotubes modified electrode of single nanometer platinum, has higher electro catalytic activity and anti-CO toxic, is with a wide range of applications in the photoelectrocatalysis field.
Description of drawings
Fig. 1: the pulse waveform synoptic diagram in the electrodeposition process.
Fig. 2: specific embodiment 1 makes the catalysis methanol CV curve of electrode.
Fig. 3: specific embodiment 2 makes the catalysis methanol CV curve of electrode.
Fig. 4: specific embodiment 3 makes the catalysis methanol CV curve of electrode.
Fig. 5: specific embodiment 4 makes the catalysis methanol CV curve of electrode.
Fig. 6: specific embodiment 2 makes the surperficial SEM shape appearance figure of electrode.
Fig. 7: specific embodiment 2 makes the energy spectrogram of electrode.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to following examples.In order to make test data have comparability, so under identical test condition variant catalyzer is carried out the cyclic voltammetric test, i.e. test condition unification is:
Counter electrode: platinum electrode;
Reference electrode: saturated calomel electrode;
Electrolytic solution: 0.5M H
2SO
4+ 1M CH
3The solution of OH
Electric potential scanning speed=50mV/s;
After example 1, the TA1 titanium plate surface processing with 1cm*1cm, (surface treatment is about to the titanium sheet after the sand paper polishing, removes surface and oil contaminant with the acetone ultrasonic cleaning, puts into the alcohol ultrasonic cleaning again, and is clean with distilled water flushing then, makes electrode after the drying.Following examples is all identical) put into and contain 1g/L NH
4HF
2, 50g/L H
2The ethylene glycol solution of O at constant voltage 60V, carries out anodic oxidation 1h under 10 ℃ of the temperature, during continuous mechanical stirring.The TiO that makes
2Nanotube is heat-treated under 500 ℃, and the time is 2h, furnace cooling.TiO after the high-temperature heat treatment
2Nanotube is put into the mixed aqueous solution that contains 4.0mM Platinic chloride, 4.0mM ruthenium trichloride and 0.5M sulfuric acid, and negative electrode, pulse anode current density are respectively-250mA/cm, 250mA/cm
2, the cathode pulse ON time is 6ms, anodic pulse ON time 1ms, and turn-off time 1s, electrodeposition time are 15min, namely make the working electrode electrode.Adopt cyclic voltammetry in three electrode test systems, to carry out the catalytic oxidation of methyl alcohol, record CV curve such as Fig. 2.
After example 2, the TA1 titanium plate surface processing with 1cm*1cm, (surface treatment is about to the titanium sheet after the sand paper polishing, removes surface and oil contaminant with the acetone ultrasonic cleaning, puts into the alcohol ultrasonic cleaning again, and is clean with distilled water flushing then, makes electrode after the drying.Following examples is all identical) put into and contain 3g/L NH
4HF
2, 100g/L H
2The ethylene glycol solution of O at constant voltage 30V, carries out anodic oxidation 4h under 20 ℃ of the temperature, during continuous mechanical stirring.The TiO that makes
2Nanotube is heat-treated under 450 ℃, and the time is 4h, furnace cooling.TiO after the high-temperature heat treatment
2Nanotube is put into the mixed aqueous solution that contains 4.0mM Platinic chloride, 1.0mM ruthenium trichloride, 0.5M sulfuric acid, and negative electrode, pulse anode current density are respectively-350mA/cm, 350mA/cm
2, negative electrode, anodic pulse ON time are 2ms, and turn-off time 1s, electrodeposition time are 10min, namely make the working electrode electrode.Adopt cyclic voltammetry in three electrode test systems, to carry out the catalytic oxidation of methyl alcohol, record CV curve such as Fig. 3.
After example 3, the TA1 titanium plate surface processing with 1cm*1cm, (surface treatment is about to the titanium sheet after the sand paper polishing, removes surface and oil contaminant with the acetone ultrasonic cleaning, puts into the alcohol ultrasonic cleaning again, and is clean with distilled water flushing then, makes electrode after the drying.Following examples is all identical) put into and contain 5g/L NH
4HF
2, 200g/L H
2The ethylene glycol solution of O at constant voltage 10V, carries out anodic oxidation 6h under 30 ℃ of the temperature, during continuous mechanical stirring.The TiO that makes
2Nanotube is heat-treated under 350 ℃, and the time is 4h, furnace cooling.TiO after the high-temperature heat treatment
2Nanotube is put into the mixed aqueous solution that contains 1.0mM Platinic chloride, 0.5mM ruthenium trichloride, 0.5M sulfuric acid, and negative electrode, pulse anode current density are respectively-350mA/cm, 350mA/cm
2, negative electrode, anodic pulse ON time are 1ms, and turn-off time 1s, electrodeposition time are 25min, namely make working electrode.Adopt cyclic voltammetry in three electrode test systems, to carry out the catalytic oxidation of methyl alcohol, record CV curve such as Fig. 4.
After example 4, the TA1 titanium plate surface processing with 1cm*1cm, (surface treatment is about to the titanium sheet after the sand paper polishing, removes surface and oil contaminant with the acetone ultrasonic cleaning, puts into the alcohol ultrasonic cleaning again, and is clean with distilled water flushing then, makes electrode after the drying.Following examples is all identical) put into and contain 3g/L NH
4HF
2, 50g/L H
2The ethylene glycol solution of O at constant voltage 40V, carries out anodic oxidation 2h under 20 ℃ of the temperature, during continuous mechanical stirring.The TiO that makes
2Nanotube is heat-treated under 400 ℃, and the time is 3h, furnace cooling.Put into the mixed aqueous solution that contains 4.0mM Platinic chloride, 10mM ruthenium trichloride, 0.5M sulfuric acid, negative electrode, pulse anode current density are respectively-50mA/cm, 50mA/cm
2, the cathode pulse ON time is 2ms, anodic pulse ON time 4ms, and turn-off time 1s, electrodeposition time are 5min, namely make the working electrode electrode.Adopt cyclic voltammetry in three electrode test systems, to carry out the catalytic oxidation of methyl alcohol, record CV curve such as Fig. 5.
The pulse electrodeposition parameter of the different preparation conditions of table 1 (embodiment 1-4)
The performance perameter of the different electrodes of table 2 (embodiment 1-4) catalysis methanol
Claims (2)
1. a pulse electrodeposition prepares the method for the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium, it is characterized in that preparation process may further comprise the steps:
1) with the titanium sheet after sand paper polishing, remove surface and oil contaminant with the acetone ultrasonic cleaning, put into the alcohol ultrasonic cleaning again, clean with distilled water flushing then, dry afterwards as electrode basement;
2) adopt constant voltage dc anodizing legal system to be equipped with titania nanotube.Be anode with the titanium sheet, graphite is negative electrode, and electrolytic solution is for containing 1～5g/L NH
4HF
2, 50～200g/L H
2The ethylene glycol solution of O, temperature is controlled at 10～30 ℃, voltage is set to 10～60V, the time is 1～6h, during adopt magnetic agitation;
3) TiO that makes
2Nanotube is heat-treated under 350～500 ℃, and the time is 1～4h, furnace cooling.
4) with TiO
2Nanotube is working electrode, pure platinum electrode is counter electrode, immerse platinum, ruthenium molar concentration rate and be in the electrolytic solution of 4:1～1:4 and carry out pulse electrodeposition, pulse waveform is: pulse cathode current density is-350～-50mA/cm, pulse anode current density are 50～350mA/cm
2, negative electrode, anodic pulse ON time are 1～6ms, and turn-off time 1s, electrodeposition time are 5～25min, and temperature is room temperature, and deposition process adopts magnetic agitation;
5) after deposition finishes, with distilled water flushing, dry up, make the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium.
2. the method for preparing the TiO 2 nanotubes modified electrode of nanometer platinum/ruthenium according to the described a kind of pulse electrodeposition of claim 1, it is characterized in that the deposited electrolyte that step 4) is prepared is the mixed aqueous solution that contains 1.0～4.0mM Platinic chloride, 0.5～10mM ruthenium trichloride, 0.5M sulfuric acid.
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Cited By (4)
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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 |
| CN106637334A (en) * | 2016-09-26 | 2017-05-10 | 首都师范大学 | Method for adjusting and controlling proportion and chemical properties of impurity elements in valve metal anodic oxide film and product obtained through method |
| CN107012494A (en) * | 2017-03-16 | 2017-08-04 | 东北大学 | The method that one-step method prepares the metal oxide supported nanocatalyst by matrix of metal or alloy |
| CN112779557A (en) * | 2019-11-07 | 2021-05-11 | 韩国科学技术研究院 | Method for modifying electrode for electrochemical reaction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106637334A (en) * | 2016-09-26 | 2017-05-10 | 首都师范大学 | Method for adjusting and controlling proportion and chemical properties of impurity elements in valve metal anodic oxide film and product obtained through method |
| CN107012494A (en) * | 2017-03-16 | 2017-08-04 | 东北大学 | The method that one-step method prepares the metal oxide supported nanocatalyst by matrix of metal or alloy |
| 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 |
| CN112779557A (en) * | 2019-11-07 | 2021-05-11 | 韩国科学技术研究院 | Method for modifying electrode for electrochemical reaction |
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