Stability of bimetallic Pd–Zn catalysts for the steam reforming of methanol

ZnO-supported palladium-based catalysts have been shown in recent years to be both active and selective towards the steam reforming of methanol, although they are still considered to be less active than traditional copper-based catalysts. The activity of PdZn catalysts can be significantly improved by supporting them on alumina. Here we show that the Pd/ZnO/Al2O3 catalysts have better long-term stability when compared with commercial Cu/ZnO/Al2O3 catalysts, and that they are also stable under redox cycling. The Pd/ZnO/Al2O3 catalysts can be easily regenerated by oxidation in air at 420 °C followed by re-exposure to reaction conditions at 250 °C, while the Cu/ZnO based catalysts do not recover their activity after oxidation. Reduction at high temperatures (>420 °C) leads to Zn loss from the alloy nanoparticle surface resulting in a reduced catalyst activity. However, even after such extreme treatment, the catalyst activity is regained with time on stream under reaction conditions alone, leading to highly stable catalysts. These findings illustrate that the nanoparticle surface is dynamic and changes drastically depending on the environment, and that elevated reduction temperatures are not necessary to achieve high CO2 selectivity.