Partial Oxidation of Bio-methane over Nickel Supported on MgO-ZrO2 Solid Solutions.

Syngas can be produced from biomethane via Partial Oxidation of Methane (POM), being an attractive route since it is ecofriendly and sustainable. In this work, catalysts of Ni supported on MgO-ZrO2 solid solutions, prepared by a one-step polymerization method, were characterized by HRTEM/EDX, XRD, XPS, H2-TPR, and in situ XRD. All catalysts, including Ni/ZrO2 and Ni/MgO as reference, were tested for POM (CH4:O2 molar ratio 2, 750 ºC, 1 atm). NiO/MgO/ZrO2 contained two solid-solutions, MgO-ZrO2 and NiO-MgO, as revealed by XRD and XPS. Ni (30 wt%) supported on MgO-ZrO2 solid solution exhibited high methane conversion and hydrogen selectivity. However, depending on the MgO amount (0, 4, 20, 40, 100 molar percent) major differences in NiO reducibility, growth of Ni0 crystallite size during H2 reduction and POM, and in carbon deposition rates were observed. Interestingly, catalysts with lower MgO content achieved the highest CH4 conversion (~ 95%), high selectivity to H2 (1.7) and CO (0.8), and low carbon deposition rates (0.024 g carbon.gcat-1 h-1) with Ni4MgZr (4 mol% MgO) turning out to be the best catalyst. In situ XRD during POM indicated metallic Ni nanoparticles (average crystallite size of 31 nm), supported by MgO-ZrO2 solid solution, with small amounts of NiO-MgO being present as well. The presence of MgO also influenced the morphology of the carbon deposits, leading to filaments instead of amorphous carbon. A combustion-reforming mechanism is suggested and using a MgO-ZrO2 solid solution support strongly improves catalytic performance, which is attributed to effective O2, CO2 and H2O activation at the Ni/MgO-ZrO2 interface.

In situ study of copper reduction in SrTi1-xCuxO3 nanoparticles.

Perovskite strontium titanate is a promising functional material for gas sensors and catalysis applications. Herein, we report the preparation of SrTi1-xCuxO3 nanoparticles with Cu doped in the B sites using a modified polymeric precursor method. This study describes in detail the structural and local atomic configurations for the substitution of Cu into the titanium sites and its reducibility using X-ray diffraction (XRD), field emission gun scanning and transmission electron microscopies (FEG-SEM and TEM), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) analyses. Our results indicate that copper is segregated for x≥ 0.06. After exposing the samples to a hydrogen-rich atmosphere at temperatures over 500 K, copper is reduced from Cu(2+) to metallic Cu. This reduction was attributed to copper atoms that originated primarily from the CuO phase.