Metal–Organic Frameworks for Sustainable Photocatalytic and Electrocatalytic HMF‐to‐FDCA Conversion: From Catalyst Engineering to Energy‐Saving Paired Electrolysis Systems

ABSTRACT Photocatalytic and electrocatalytic upgrading of lignocellulosic biomass into value‐added chemicals offers a sustainable route to carbon neutrality. 5‑hydroxymethylfurfural (HMF) is a key intermediate because its selective oxidation yields 2,5‑furandicarboxylic acid (FDCA), a renewable monomer for biodegradable polyesters. This review summarizes metal–organic frameworks (MOFs)‐based catalysts for photo‐ and electrochemical HMF oxidation, covering pristine MOFs and MOF‐derived catalytic systems. This review further discusses key modification strategies, including dynamic structural regulation, multi‐active‐site design, and derivative structural optimization. Through these strategies, MOF‐based systems modulate electronic structure, active‐site accessibility, and mass/charge transport, thereby enhancing the activity and FDCA selectivity of photocatalytic and electrocatalytic HMF oxidation. Building on this mechanistic understanding, we examine the structure–activity relationships and reaction mechanisms revealed by in situ characterizations and density functional theory calculations. This review also assesses paired electrolysis systems that integrate anodic HMFOR with cathodic hydrogen evolution or other value‐added reductions. Finally, persistent challenges such as scalable synthesis and reactor design are addressed, along with future perspectives for rational catalyst design and industrial implementation of MOF‐based biomass upgrading.