Advances in Heterogeneous Catalysis for Hydrogen Production via Steam Reforming of Biomass-Derived Alcohols: Catalytic Structure-Activity Relationships from Ethanol to Glycerol Systems
Steam reforming of biomass-derived alcohols (ethanol, ethylene glycol, glycerol, etc.) represents a critical pathway for sustainable hydrogen energy systems. This review systematically examines recent advances in heterogeneous catalysis, elucidating structure-performance correlations between alcohol molecular structures and catalyst requirements. Ethanol is prone to dehydration and methanation side reactions, while ethylene glycol leverages its dihydroxy structure to enhance dehydrogenation and C–C cleavage, improving H2 selectivity. In contrast, glycerol suffers from intensified reaction network complexity and carbon-induced deactivation due to its trihydroxy configuration. The unified catalyst design strategy involves precisely modulating metal electronic structures (e.g., alloying/atomic-level dispersion) and support oxygen mobility (e.g., rare-earth modification) to synergistically optimize dehydrogenation and carbon resistance. Ni-based catalysts dominate owing to low cost and high C–C bond activation capability, yet their stability requires synergistic enhancement via alloying (Fe, Co, Cu, etc.) or rare-earth modification (Ce, Pr, La, etc.). Noble metal systems (Pt, Rh, Ir, etc.) exhibit low-temperature activity advantages, but are transitioning strategically toward single-atom catalysis and high-entropy-oxide-based multicomponent architectures under cost constraints. Future efforts are suggested to integrate in situ/operando characterization with theoretical modeling to uncover dynamic structure-activity relationships, establish elementary reaction databases for data-driven rational catalyst design, and achieve cross-scale catalyst-reactor synergy, thereby providing a scientific foundation for efficient sustainable hydrogen production.