La0.75Sr0.25XO3 (X = Fe, Mn or Cr) with coking tolerance for CH4/H2O reaction: effect of H2S on catalytic performance

The influence of the B type cation from the ABO3 perovskite formulation La0.75Sr0.25XO3 (LSX, where X is Fe, Mn or Cr) on the C and H2S tolerance and its catalytic activity for the methane/water reaction has been studied. The samples were prepared by a simple and cost-efficient citrate method. The exhaustive characterization of the bulk and surface properties of the catalysts has been accomplished by means of complementary methods: nitrogen adsorption–desorption isotherm measurements, XRD, TPR and XPS. Their catalytic properties in CH4/H2O reactions (CH4/H2O molar ratios of 10 and 1) were studied in the presence and absence of H2S in order to evaluate their potential use as anode materials in solid oxide fuel cells operated on natural gas. Before addition and upon suppression of H2S, the activity varied in the following order: LSF > LSM ≫ LSC. This correlates with the oxygen mobility determined by TPR. A strong promoting effect of H2S on the catalytic activity is observed for LSC, which makes this sample the most active of the series, while H2S has a weak influence on the other perovskites. The oxygen vacancies and the presence of S2− were identified as being responsible for the enhanced catalytic activity upon H2S addition.