Sputtered Cu-doped NiO thin films as an efficient electrocatalyst for methanol oxidation.

The efficient electrocatalysts for direct methanol oxidation play an essential role in the electrochemical energy conversion systems for their application in a wide range of portable applications. Consequently, Cu-doped NiO thin films on fluorine-doped tin oxide (FTO) were successfully prepared by the co-sputtering deposition technique, using various deposition times (300, 600, 900, and 1200 seconds), and producing films of different thicknesses (30, 55, 90, and 120 nm, respectively). X-ray diffraction (XRD) revealed the ideal crystallinity of the structure of the prepared films and was used to observe the effect of the thickness of the films on the crystal size. Energy-dispersive X-ray spectroscopy (EDS) confirmed the purity of the deposited film without any contamination. Field emission scanning electron microscopy (FESEM) images confirmed the film thickness increase with increasing deposition time. The surface roughness value of the Cu-NiO 1200 film was found to be 3.2 nm based on the atomic force microscopy (AFM) measurements. The deposited thin films of different thicknesses have been used as electrocatalysts for methanol oxidation at various concentrations of methanol (0, 0.5, 1, and 2 M), and displayed the highest electrocatalytic performance in 1 M methanol. Cu-doped NiO thin films have the advantage as electrocatalysts where they can be used directly without adding any binder or conducting agents, this is because Cu-doped NiO is deposited with high adhesion and strong electrical contact to the FTO substrate. A clear impact on the catalytic activity with increasing film thickness and a correlation between the film thickness and its catalytic activity was observed. The current density increased by about 60% for the Cu-NiO 1200 sample compared to Cu-NiO 300 sample, with the lowest onset potential of 0.4 V Ag/AgCl. All deposited thin films of different thicknesses exhibited high stability at 0.6 V in 1 M methanol. This will open the window toward using physical deposition techniques for optimizing the electrocatalytic activity of different catalysts for electrocatalytic applications.