Biomass Electrorefining: Electrical‐to‐Chemical Energy Relay Systems for Hydrogen‐Chemical Coproduction via Multi‐Reaction Electrocatalytic Cascades

ABSTRACT As nature's most abundant renewable carbon source, biomass enables a closed–loop carbon‐neutral paradigm for producing industrial oxygenates. Biomass electrocatalytic oxidation reaction (BOR) replaces the energy‐intensive oxygen evolution reaction (OER), simultaneously achieving green synthesis of value‐added oxygenates and enhancing electrolytic energy efficiency, thereby displacing fossil–based production routes. This review systematically elucidates the electrocatalytic conversion of biomass derivatives (e.g., alcohols, furanal, and sugars, etc.) into value‐added products coupled with hydrogen production from the perspectives of catalyst design principles and reaction mechanisms. Further focus on integrated anode–cathode systems that synergistically couple biomass oxidation with cathodic carbon dioxide reduction (for fuel synthesis) or nitrate reduction (for ammonia production and pollutant remediation), overcoming limitations of standalone hydrogen generation while enabling coproduction of chemicals and carbon/nitrogen resource cycling. Advanced multi‐field coupling strategies are analyzed for their efficacy in enhancing reaction selectivity and efficiency, including photo‐electrocatalysis to excite charge carriers, thermo‐electrocatalysis to optimize kinetics, and high‐pressure electrocatalysis to regulate mass transfer. Future efforts should prioritize non‐precious metal active site engineering and scalable reactor design to advance biomass refining from conceptual frameworks toward industrial implementation.