Understanding the Role of Surface Oxygen in Hg Removal on Un-Doped and Mn/Fe-Doped CeO2 (111).

Effects of surface-adsorbed O and lattice O for the CeO2 (111) surface on Hg removal has been researched. In this work, periodic calculations based on density functional theory (DFT) were performed with the on-site Coulomb interaction. Hg is oxidized to HgO via the surface-adsorbed O by overcoming a Gibbs free energy barrier of 114.1 kJ·mol-1 on the CeO2 (111) surface. Mn and Fe doping reduce the activation Gibbs free energy for the Hg oxidation, and energies of 70.7 and 49.6 kJ·mol-1 are needed on Ce0.96 Mn0.04 O2 (111) and Ce0.96 Fe0.04 O2 (111) surfaces. Additionally, lattice O also plays an important role in Hg removal. Hg cannot be oxidized leading to the formation of HgO on the un-doped CeO2 (111) surface owing to the inertness of lattice O, which can be easily oxidized to HgO on Ce0.96 Mn0.04 O2 (111) and Ce0.96 Fe0.04 O2 (111) surfaces. It can be seen that both surface-adsorbed O and lattice O play important roles in removing Hg. The present study will shed light on understanding and developing Hg removal technology on un-doped and Mn/Fe-doped CeO2 (111) catalysts. © 2019 Wiley Periodicals, Inc.

Photocatalytic decomposition of methanol over La/TiO2 materials.

Lanthanum-modified TiO2 photocatalysts (0.2-1.5 wt% La) were investigated in the methanol decomposition in an aqueous solution. The photocatalysts were prepared by the common sol-gel method followed by calcination. The structural (X-ray diffraction, Raman, X-ray photoelectron spectroscopy), textural (N2 physisorption), and optical properties (diffuse reflectance spectroscopy, photoelectrochemical measurements) of all synthetized nanomaterials were correlated with photocatalytic activity. Both pure TiO2 and La-doped TiO2 photocatalysts proved higher yields of hydrogen in comparison to photolysis. The photocatalyst with optimal amount of lanthanum (0.2 wt% La) showed almost two times higher amount of hydrogen produced at the same time as in the presence of pure TiO2. The photocatalytic activity increased with both increasing photocurrent response and decreasing amount of lattice and surface O species. It has been shown that both direct and indirect mechanisms of methanol photocatalytic oxidation participate in the production of hydrogen. Both direct and indirect mechanisms take part in the formation of hydrogen.