Elucidating the effect of barium halide promoters on La2O3/CaO catalyst for oxidative coupling of methane

The industrialization of oxidative coupling of methane (OCM) is restricted by the low once through yield of C2 hydrocarbons. Recently, the halogen-assisted OCM process has been attempted to overcome this issue, but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides. In this work, the barium salts, particularly barium halides (BaCl2 and BaF2), were demonstrated to be efficient promoters to improve the OCM reactivity of La2O3/CaO catalyst by increasing both C2 selectivity and C2H4/C2H6 ratio, and simultaneously achieving outstanding reaction stability. The promoting mechanism can be understood in two aspects. On the one hand, the introduction of barium salts increased the amount of surface electrophilic oxygen species, serving as the alkaline active sites for selective methane activation. On the other hand, the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C2H6 dehydrogenation, and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability. This work not only provides a class of efficient OCM catalyst, but also offers a highly stable halogen-assisted reaction strategy.