Advances in catalysts for production of renewable H2/CH4 by Aqueous Phase Reforming (APR) of biomass-derived oxygenates

• Advances in catalysts for APR of biomass-derived oxygenates are critically reviewed. • Tailored activity in APR via noble and non-noble metal catalysts is explained. • Catalyst structure–activity relationships in APR are systematically discussed. • Reaction mechanisms of APR into H 2 /CH 4 with model oxygenates are analyzed. • Future directions in APR catalyst development and scale-up are outlined. Aqueous phase reforming (APR) of biomass-derived oxygenates has emerged as a versatile and sustainable route for producing renewable hydrogen (H 2 ) and methane (CH 4 ) under relatively mild conditions (200–300 °C and 1.5–5 MPa). This review highlights recent progress in understanding and optimizing APR, with particular attention to catalyst development, reaction mechanisms, and process design strategies that influence product selectivity. Model compounds such as methanol, ethanol, ethylene glycol, and glycerol serve as representative substrates to probe the complex network of dehydrogenation, C–C and C–O bond scission, water-gas shift (WGS), and methanation reactions. Advances in catalyst design, ranging from noble metals (e.g., Pt, Pd) paired with oxygen-vacancy-rich or hydroxylated/acidic/basic supports, to non-noble systems (e.g., Ni–Sn, Ni–Cu, N-doped carbons), are discussed in terms of their ability to tune the H 2 /CH 4 production. While certain catalysts promote reforming and WGS to favor hydrogen, others bias the route toward methanation, revealing the catalyst as a key variable for this reaction, in addition to the influence of conditions such as pressure and temperature. Finally, the identified challenges and outlined future directions highlight the potential of APR as a flexible and scalable technique for renewable fuel production, enabling on-demand tuning between green hydrogen and renewable natural gas.