Enhancing the Catalytic Activity of Lanthanum-Ceria Fluorite for Methane Conversion in SOFC

Abstract

A2B2O7 compounds have unique properties, such as good thermal stability, oxygen mobility, ionic conductivity, etc. Such compounds with tailored compositions exhibit good catalytic properties in a variety of high-temperature reactions, such as reform and oxidative coupling of methane (OCM). An effective catalyst for OCM must have electrophilic oxygen mobility and alkalinity on its surface. A typical A2B2O7 compound that contains a trivalent rare earth metal at site A, such as La, can provide the necessary surface alkalinity for a good OCM catalyst. Previous studies show that La2Ce2O7 (LCO) catalysts perform well in OCM due to the selective mobile oxygen sites, suitable alkaline sites, and high thermal stability. Doping LCO with Ca increases the alkalinity, which can considerably increase selectivity for ethylene in the OCM reaction. We have studied calcium-doped lanthanum ceria materials as a catalytic layer in solid oxide fuel cells reactors for methane conversion to ethylene. We have explored the combustion synthesis to obtain homogeneous La2-xCaxCe2O7 powders with x = 0, 0.25, and 0.50 (LCO, LCa25, and LCa50, respectively). X-ray diffraction (XRD) showed that the calcium addition in LCO formed a single-phase solid solution. The crystalline structure of the synthesized materials is the disordered fluorite-type, as indicated by both XRD and Raman analysis. Raman spectroscopy data evidenced the presence of surface oxygen vacancies on all materials, which may benefit the OCM reaction. SEM images of as-prepared powders obtained evidenced a similar microstructure composed of porous sponge-like agglomerated particles with irregular shape, expected from the combustion synthesis (Fig. 1). Ca-doping changed the sintering behavior by reducing the onset of shrinkage during the sintering process. Impedance spectroscopy data showed increased ionic conductivity with increasing Ca-doping. Such an increase is more evident at high measuring temperature (800 oC) and indicates enhanced oxygen mobility that are expected to contribute to OCM reaction.Figure 1: Scanning electron microscope micrographs of La2-xCaxCe2O7 (x = 0, 0.25, and 0.50) as-prepared powders obtained by combustion method. Figure 1