Catalytic Steam Reforming of Methanol, Ethanol, and Glycerol for Hydrogen Production: A Critical Review of Reaction Chemistry, Catalyst Design, Performance Metrics, and Deactivation

Catalytic steam reforming of oxygenated feedstocks is an important route to hydrogen-rich gases, but methanol, ethanol, and glycerol differ substantially in C–C bond content, reaction-network complexity, catalyst requirements, and deactivation behavior. This critical review compares the three feedstocks using feedstock-specific reaction chemistry rather than a generalized reforming mechanism. The stoichiometric maxima for complete conversion to CO2 and H2 are 3, 6, and 7 mol H2 per mol of methanol, ethanol, and glycerol, respectively, but these limits are not treated as experimental catalyst rankings. Cu-based systems dominate low-temperature methanol steam reforming, whereas Ni-, Co-, bimetallic, noble-metal, and perovskite-derived catalysts are prominent in ethanol and glycerol reforming, where C–C activation and carbon suppression become increasingly important. Emphasis is placed on the nature and evolution of active sites, metal–support interactions, carbon deposition, sintering, regeneration, and the distinction among conversion, H2 yield, H2 selectivity, and dry-gas H2 concentration. Recent studies through 2026 are integrated with foundational mechanistic work to identify catalyst-design principles and evidence gaps relevant to durable hydrogen production.