Robust Ruthenium-Saving Catalyst for High-Temperature Carbon Dioxide Reforming of Methane

Dry reforming of methane (DRM) integrates resourceful utilization of unwanted CO2 using cheap methane and storage of renewable energy. High temperature favors the highly endothermic process, while catalyst thermal deterioration is a major obstacle. Here we report a robust Ru/MgAl2O4 catalyst prepared via physical vapor deposition method that exhibits 1 or 2 orders of magnitude higher activity than conventional ruthenium or nickel catalysts. Importantly, instead of deactivation or coke deposition, the catalyst demonstrates a surprising activity increase by 1.5 times after reaction at 850 °C for 600 h. Ru initially was dispersed as isolated atoms on MgAl2O4, then condensed into unfaceted clusters (1.1 nm), and finally retained as faceted nanoparticles (NPs, 2.7 nm) upon testing, becoming more and more active by decreasing the barrier of breaking the C–H bond of methane. The low Ru content (0.15 wt %) and high space-time yield make it cost-competitive to regeneration-required nickel catalysts, paving a way to develop affordable commercial precious metal catalyst.