Fabrication and Significant Photoelectrochemical Activity of Titania Nanotubes Modified with Thin Indium Tin Oxide Film

doi:10.1007/s40195-017-0653-9

Abstract

Abstract:

Ordered titanium dioxide nanotubes (TiO₂NTs) modified with indium tin oxide (ITO) films were obtained via magnetron sputtering, in which ITO plate was used as a target, onto the as-anodized titania support followed by the calcination process. The morphology of fabricated material with deposited oxide was investigated using scanning electron microscopy. Raman and UV-Vis spectroscopies were utilized to characterize crystalline phase and optical properties of prepared samples, whereas X-ray photoelectron spectroscopy allowed determining the binding energy of present elements. In the case of titanium, three various oxidation states were identified and also the presence of indium and tin was confirmed. The electrochemical test carried out when the sample was exposed to light allows for selection of the most photoactive material. The highest photocurrent was registered when only 5-nm ITO layer was sputtered, and it equals 256 and 133 μA cm^-2 for the electrode material immersed in 0.5 M KOH and K₂SO₄ electrolytes, respectively, that is accordingly 3.5 and 4.4 times higher than the one observed for pristine titania. Furthermore, ITO-modified titania exhibits excellent photostability upon prolonged illumination that is of key importance for possible application in light-driven processes.

Key words: Titania nanotubes, Indium tin oxide, Photoactivity, Anodization, Magnetron sputtering, Electrochemical activity

Katarzyna Siuzdak, Mariusz Szkoda, Jakub Karczewski, Jacek Ryl, Kazimierz Darowicki, Katarzyna Grochowska. Fabrication and Significant Photoelectrochemical Activity of Titania Nanotubes Modified with Thin Indium Tin Oxide Film[J]. Acta Metallurgica Sinica (English Letters), 2017, 30(12): 1210-1220.

Figures/Tables 14

Fig. 1 SEM images of a pristine TiO2NTs surface, b its cross-section, c TiO2NT-ITO-5, d TiO2-ITO-10

Fig. 2 Raman spectra of pristine and ITO-modified titania nanotubes

Fig. 3 XRD spectra registered for pristine and ITO-modified titania nanotubes

Fig. 4 Absorbance spectra and the transformation of Kubelka-Munk plot versus photon energy of obtained samples (inset)

Fig. 5 XPS survey spectrum registered for TiO2-ITO-5

Fig. 6 High-resolution XPS spectra recorded at: a indium, b tin, c titanium, d oxygen, e carbon binding energy region of TiO2-ITO-5

Fig. 7 EDX spectrum of TiO2-ITO-5 sample

Fig. 8 Cyclic voltammetry curves of pristine titania and TiO2NTs modified with different ITO films (electrolyte 0.5 M K2SO4, v = 50 mV/s)

Fig. 9 Linear sweep voltammograms under different photoanodes: pristine TiO2NTs and ITO-modified TiO2NTs in 0.5 M K2SO4 (v = 10 mV/s)

Fig. 10 Impedance spectra registered at the resting potential for pristine TiO2NTs and titania modified with 5 and 7.5 nm of ITO immersed in 0.5 M K2SO4

Fig. 11 Transient photocurrent responses of TiO2NTs with and without ITO coverage in a 0.5 M K2SO4 and b 0.5 M KOH (E = + 0.5 V vs. Ag/AgCl/0.1 M KCl)

Table 1 Photocurrent values obtained for investigated electrode materials under UV-Vis illumination after 300 s of measurements in 0.5 M K2SO4 and 0.5 M KOH (E = + 0.5 V vs. Ag/AgCl/0.1 M KCl)

0.5 M K₂SO₄			0.5 M KOH
Sample	J (μAcm^-2)	EF	J (μAcm^-2)	EF
TiO₂	30	1	73	1
TiO₂-ITO-2.5	62	2.1	157	2.1
TiO₂-ITO-5	133	4.4	256	3.5
TiO₂-ITO-7.5	81	2.7	204	2.8
TiO₂ ITO-10	83	2.8	197	2.7

Fig. 12 Time-dependent photocurrent density of TiO2-ITO-5 sample under continuous simulated sunlight illumination (> 4 h) registered in 0.5 M KOH at +0.5 V vs. Ag/AgCl/0.1 M KCl

Fig. 13 Energy band scheme depicting the photoexcitation and charge transfer within the SnO2/InO3/TiO2 heterojunction

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