Nitrogen-doped TiO (N-TiO) is considered as one of the most promising materials for various photocatalytic applications, while noble metals Pd and Pt are known as good catalysts for hydrogen evolution. This work focuses on the determination of structural and electronic modifications of N-TiO, achieved by noble metal deposition at the surface, as a starting indicator for potential applications. We focus on the properties of easily synthesized nanocrystalline nitrogen-doped anatase TiO, modified by depositing small amounts of Pd (0.05 wt%) and Pt (0.10 wt%), aiming to demonstrate efficient enhancement of optical properties. The chemical states of dopants are studied in detail, using X-ray photoemission spectroscopy, to address the potential of N-TiO to act as a support for metallic nanoparticles. DFT calculations are used to resolve substitutional from interstitial nitrogen doping of anatase TiO, as well as to study the combined effect of nitrogen doping and oxygen vacancy formation. Based on the binding energies calculated using Slater's transition state theory, dominant contribution to the N 1s binding energy at 399.8 eV is ascribed to interstitially doped nitrogen in anatase TiO. Given that both structure and photocatalytic properties depend greatly on the synthesis procedure, this work contributes further to establishing correlation between the structure and optical properties of the noble metal modified N-TiO system.
Nickel containing perovskite type oxides have been reported within the most active materials for OER in alkaline media and also with good electrocatalysts properties for OOR. The increase of the bifunctional character of these materials is the subject of research in view of the need for alternatives to noble materials and to the paramount importance of electrode development for the next generation of regenerative fuel cells. The LaNiO 3 oxide was prepared by a self-combustion method using citric acid. The electrodes were prepared by coating a nickel foam support with an oxide suspension. Electrochemical characterization was carried out by Cyclic Voltammetry (CV) and Electrochemical Impedance (EI). The electrode's roughness factor has been estimated from the charging currents (i c ) recorded between -0.050 V and +0.050 V (Fig 1-a). From the linear variation between the i c vs sweep rate (sr), the double layer capacitance of 0.208±0.015 µF cm -2 was calculated (Fig 1-b). EI spectra were fitted to an equivalent circuit that rendered capacity values in agreement with those estimated by CV.The oxide coating roughness factor was estimated as 3463±250, representing a much higher value than those reported in the literature [1,2] for the same oxide. This enhancement of the electrodes roughness can be associated with the oxide preparation method associated with the use of Ni foam as the oxide support. AcknowledgementsThis work is partially financed by Fundação para a Ciência e Tecnologia (FCT), under contract nº PTDC/CTM/102545/2008.
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