Synergetic effect of graphene and Co(OH)2 as cocatalysts of TiO2 nanotubes for enhanced photogenerated cathodic protection

doi:10.1016/j.jmst.2019.07.034

Abstract

Abstract:

A layer of graphene (GR) particles was successfully deposited at the interface between Co(OH)₂ nanoparticles and TiO₂ nanotubes, aiming to improve the photoelectrochemical performance of the large-bandgap semiconductor TiO₂. The obtained Co(OH)₂/GR/TiO₂ was extensively characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis absorption spectra and photoluminescence (PL) emission spectra. Electrochemical impedance spectra, photogenerated potential-time (E-t) photocurrent density-time (i-t) and i-E curves and open circuit potential (OCP) curves were measured to investigate the photoelectrochemical activities and photogenerated cathodic protection properties. The results revealed that Co(OH)₂/GR/TiO₂ exhibits excellent photoelectrochemical and photogenerated cathodic performance due to synergistic effect between Co(OH)₂ and graphene. Co(OH)₂ and graphene co-modified TiO₂ photoanode could provide an effective protection for 304 stainless steel (304SS) in 3.5 wt% NaCl solution for 12 h, which would be promising for future practical applications in the field of marine corrosion protection.

Key words: TiO₂ nanotubes, Graphene, Co(OH)₂ nanoparticles, Photoelectrochemical performance, Photogenerated cathodic protection

Xiayu Lu, Li Liu, Xuan Xie, Yu Cui, Emeka E. Oguzie, Fuhui Wang. Synergetic effect of graphene and Co(OH)₂ as cocatalysts of TiO₂ nanotubes for enhanced photogenerated cathodic protection[J]. J. Mater. Sci. Technol., 2020, 37: 55-63.

Figures/Tables 14

Fig. 1. Schematic illustration of preparation of Co(OH)2/GR/TiO2 nanotubes films.

Fig. 2. Raman spectrum of the graphene quantum dots.

Fig. 3. XRD patterns of (a) TiO2, (b) Co(OH)2/TiO2, (c) GR/TiO2, (d) Co(OH)2/GR/TiO2 and (e) GR.

Fig. 4. SEM images of (a) top view, (b) cross-section view of TiO2 nanotubes and (c) top view of GR/TiO2.

Fig. 5. TEM images of (a) TiO2, (b) Co(OH)2/GR/TiO2 and (c) STEM image of Co(OH)2/GR/TiO2, corresponding (d) Ti element, (e) O element and (f) Co element EDS mapping images.

Fig. 6. XPS spectra of (a) Ti 2p and (b) O 1s peaks of TiO2, GR/TiO2 and Co(OH)2/GR/TiO2, (c) C 1s peak of GR/TiO2 and (d) Co 2p peak of Co(OH)2/GR/TiO2.

Fig. 7. UV-vis (a) and visible (b) absorption spectra of the TiO2, GR/TiO2, Co(OH)2/TiO2 and Co(OH)2/GR/TiO2.

Fig. 8. PL spectra of TiO2, GR/TiO2, Co(OH)2/TiO2 and Co(OH)2/GR/TiO2 nanotubes films.

Fig. 9. Nyquist (a) and Bode (b) plots of TiO2, GR/TiO2, Co(OH)2/TiO2 and Co(OH)2/GR/TiO2 nanotubes photoelectrodes tested in 3.5?wt% NaCl solution under illumination; Schematic of the equivalent circuit obtained by EIS result fitting: (c) TiO2, GR/TiO2 and Co(OH)2/TiO2; (d) Co(OH)2/GR/TiO2.

Fig. 10. Time-based photogenerated potential for unmodified TiO2 nanotubes and Co(OH)2, GR modified TiO2 nanotubes photoelectrodes in 3.5?wt% NaCl solution under chopped illumination.

Fig. 11. Time-based photocurrent density curves for unmodified TiO2 nanotubes and Co(OH)2, GR modified TiO2 nanotubes photoelectrodes in 3.5?wt% NaCl solution under chopped illumination.

Fig. 12. Photocurrent vs. applied potential of the TiO2, GR/TiO2, Co(OH)2/TiO2 and Co(OH)2/GR/TiO2 photoelectrodes in 0.1?M Na2SO4 solution under chopped illumination.

Fig. 13. OCP curves of the four TiO2 photoelectrodes coupled with 304SS electrode in 3.5?wt% NaCl solution under 12?h long illumination.

Fig. 14. Proposed mechanism for the role of Co(OH)2/GR/TiO2 on the photogenerated cathodic protection for 304SS.

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Synergetic effect of graphene and Co(OH)₂ as cocatalysts of TiO₂ nanotubes for enhanced photogenerated cathodic protection

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