Method for preparing nano platinum/titanium dioxide nanotube electrode by pulse electrodeposition

[0022] Example 1. After surface treatment of 1.5mm*1.5mm TA1 titanium sheet, put 1g/L NH 4 HF 2 , 50g/LH 2 The ethylene glycol solution of O was anodized at a constant pressure of 10V and a temperature of 20°C for 1 hour, with constant mechanical stirring during the period. TiO 2 After the nanotubes are rinsed, they are put into an electrolyte containing 1.0~4.0mM chloroplatinic acid+0.5M sulfuric acid, and the pulse current density at the cathode is -70mA/cm 2 , The anode pulse current density is 70mA/cm 2 , The cathode pulse conduction time is 10ms, the anode pulse conduction time is 1ms, the turn-off time is 1s, and the electrodeposition time is 15min, that is, the electrode is prepared. The test of the prepared electrode to catalyze methanol is: put the electrode in 0.5M H 2 SO 4 +0.5M CH 3 In OH solution, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode is Pt-TiO 2 /Ti nanotube electrode. Before the measurement, high-purity nitrogen was introduced into the solution to remove the oxygen dissolved in the solution, and the measurement was performed under the protection of a high-purity nitrogen stream. The scanning speed of cyclic voltammetry was 50mV/s. The measured CV curve is as figure 2.

[0023] Example 2: After surface treatment of 1.5mm*1.5mm TA1 titanium sheet, put 5g/L NH 4 HF 2 , 200g/LH 2 The ethylene glycol solution of O was anodized at a constant pressure of 60V and a temperature of 30°C for 6 hours, during which time it was continuously stirred mechanically. TiO 2 After the nanotubes are rinsed, they are put into the electrolyte of 1.0~4.0mM chloroplatinic acid+0.5M sulfuric acid, and the pulse current density at the cathode is -10mA/cm 2 , The anode pulse current density is 10mA/cm 2 , The cathode pulse conduction time is 2ms, the anode pulse conduction time is 1ms, the turn-off time is 1s, and the electrodeposition time is 5min, that is, the electrode is prepared. The test of the prepared electrode to catalyze methanol is: put the electrode into 0.5MH 2 SO 4 +0.5M CH 3 In OH solution, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode is Pt-TiO 2 /Ti nanotube electrode. Before the measurement, high-purity nitrogen was introduced into the solution to remove the oxygen dissolved in the solution, and the measurement was performed under the protection of a high-purity nitrogen stream. The scanning speed of cyclic voltammetry was 50mV/s. The measured CV curve is as image 3.

[0024] Example 3: After surface treatment of 1.5mm*1.5mm TA1 titanium sheet, put 3g/L NH 4 HF 2 , 100g/LH 2 The ethylene glycol solution of O was anodized at a constant pressure of 30V and a temperature of 10°C for 2h, with constant mechanical stirring during the period. TiO 2 After the nanotubes are rinsed, they are put into the electrolyte of 1.0~4.0mM chloroplatinic acid+0.5M sulfuric acid, and the pulse current density at the cathode is -50mA/cm 2 , The anode pulse current density is 50mA/cm 2 , The cathode pulse conduction time is 6ms, the anode pulse conduction time is 1ms, the turn-off time is 1s, and the electrodeposition time is 25min, that is, the electrode is prepared. The test of the prepared electrode to catalyze methanol is: put the electrode in 0.5M H 2 SO 4 +0.5M CH 3 In OH solution, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode is Pt-TiO 2 Nanotube electrode. Before the measurement, high-purity nitrogen was introduced into the solution to remove the oxygen dissolved in the solution, and the measurement was performed under the protection of a high-purity nitrogen stream. The scanning speed of cyclic voltammetry was 50mV/s. The measured CV curve is as Figure 4.

[0025] Example 4. In specific example 3, the pulse waveform becomes: cathode pulse current density is -90mA/cm 2 , The anode pulse current density is 90mA/cm 2 , The cathode pulse on time is 8ms, the anode pulse on time is 1ms, the off time is 1s, and the electrodeposition time is 15min. The measured CV curve is as Figure 5.

[0026] Example 5. After surface treatment of 1.5mm*1.5mm TA1 titanium sheet, put 3g/L NH 4 HF 2 , 100g/LH 2 The ethylene glycol solution of O was anodized at a constant pressure of 30V and a temperature of 10°C for 2h, with constant mechanical stirring during the period. TiO 2 After the nanotubes are rinsed, they are put into an electrolyte containing 1.0~4.0mM chloroplatinic acid+0.5M sulfuric acid, and the pulse current density at the cathode is -70mA/cm 2 , The anode pulse current density is 70mA/cm 2 , The cathode pulse conduction time is 10ms, the anode pulse conduction time is 1ms, the turn-off time is 1s, and the electrodeposition time is 15min, that is, the electrode is prepared. The test of the prepared electrode to catalyze methanol is: put the electrode in 0.5M H 2 SO 4 +0.5M CH 3 In OH solution, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum electrode, and the working electrode is Pt-TiO 2 /Ti nanotube electrode. Before the measurement, high-purity nitrogen was introduced into the solution to remove the oxygen dissolved in the solution, and the measurement was performed under the protection of a high-purity nitrogen stream. The scanning speed of cyclic voltammetry was 50mV/s. The measured CV curve is as Image 6.

[0027] Table 1 Pulse waveform parameters of different preparation conditions (Examples 1-5)

[0028]

[0029] Figure 8 This is the XRD pattern of the nano-platinum/titanium dioxide nanotube electrode prepared in specific example 3 of the present invention. In the figure, 2θ of 39.861°, 46.440°, and 67.661° are the diffraction peaks of nano-Pt particles. It shows that the load is nano-Pt particles, and from the XRD diagram, it can be calculated that the particle size of the nano-Pt particles is about 11nm, indicating that the particles are fine.