Experimental and DFT study on medium entropy LaCo1/3Fe1/3Cu1/3O3 perovskite with surface-tailored for hydrogen production from methanol steam reforming

Configurational entropy engineering was employed to design perovskite catalysts for efficient hydrogen production via methanol steam reforming (MSR). The optimized medium-entropy perovskite, LaCo 1/3 Fe 1/3 Cu 1/3 O 3 , achieves an exceptionally high oxygen vacancy concentration (42.11 %), which dramatically enhances its catalytic performance. It demonstrates stable operation for over 40 h at 600 °C with high methanol conversion and hydrogen selectivity. Combined experimental and DFT studies reveal that the superior activity and low CO selectivity originate from a unique surface mechanism on the (110) facet: a high energy barrier for ∗CO desorption suppresses CO release, while a low barrier steers the reaction toward the water-gas shift pathway, favoring H 2 and CO 2 production. This work underscores the promise of entropy-engineered perovskites for durable and selective hydrogen generation.