Precision Catalysis in Dehydrogenation of Liquid Organic Hydrogen Carriers: Molecular Structure‐Geometry‐Electronic Interplay for Enhanced Hydrogen Evolution

ABSTRACT The advancement of hydrogen‐based energy systems necessitates innovative solutions for safe, efficient hydrogen storage and transportation. Liquid organic hydrogen carriers (LOHCs) emerge as a transformative technology by combining high hydrogen capacity, excellent stability, and seamless integration with existing fuel infrastructure, enabling large‐scale, long‐distance hydrogen logistics. Despite these merits, challenges in dehydrogenation kinetics and catalyst instability impede practical deployment. Herein, we present a comprehensive mechanistic review of dehydrogenation pathways across diverse LOHC platforms, including cyclohexane, methylcyclohexane, decalin, dodecahydro‐N‐ethylcarbazole, perhydro‐dibenzyltoluene/benzyltoluene, bicyclohexyl, and indole‐based LOHCs. Compared with previous reviews, this study integrates geometric and electronic effects across multiple LOHC systems to identify cross‐cutting structure–activity principles. Building on this framework, it further reveals reactant‐dependent rules for active‐site regulation, where the molecular architecture of hydrogen carriers critically determines the required catalyst characteristics. This perspective establishes a unified framework that links molecular descriptors to coordination‐specific active sites, thereby advancing precision catalyst design for next‐generation LOHC technologies.