The autothermal reforming (ATR) of methanol was performed using the Cu/ZnO/Al2O3-based catalysts for the catalytic production of hydrogen. The Cu/ZnO/Al2O3 (CZA) catalyst exhibited a high hydrogen production rate during ATR even at a low external heating temperature of 100 °C. In the O2 on/off durability test, although the hydrogen production rate of CZA gradually decreased owing to copper aggregation, the Pd-doped Cu/ZnO/Al2O3 (Pd-CZA) catalyst maintained a high hydrogen production rate. The reduction temperature of copper in Pd-CZA was found to be significantly lower than that in CZA, indicating that the reduction of copper in Pd-CZA takes place more easily. Thus, the aggregation of copper during the O2 on/off durability test was remarkably suppressed due to the fact that the reduction of copper in Pd-CZA occurred at a lower temperature than in CZA. Moreover, the Pd-CZA catalyst was self-activated under ATR conditions without the requirement for reduction pretreatment using hydrogen.

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