Poisoning‐Resistant Complete Hydrogenation of Liquid Organic Hydrogen Carriers Over Ni‐Based Inverse Catalysts

ABSTRACT Efficient hydrogen storage using liquid organic hydrogen carriers (LOHCs) requires catalysts that combine high low‐temperature activity with robustness against impure H 2 feeds. Conventional supported Ni catalysts are hindered by strong substrate adsorption and consequent site poisoning. Herein, a Ni based inverse catalyst consisting of CeZrO x clusters supported on metallic Ni is designed, which achieves >99.9% yield in the complete hydrogenation of diverse LOHCs—including mono‐, bi‐, and triphenyl‐type N‐heterocyclic and purely aromatic substrates—at low‐temperature of 130°C, exhibiting a 200‐fold higher activity than conventional Ni catalysts. Key to this performance is the oxide‐induced polarization of Ni atoms (Ni δ+ ), creating a thermodynamic stable subsurface reservoir and migration routes for dissociated H* species. Through this hydrogen transport pathway, hydrogen can efficiently hydrogenate the strongly adsorbed LOHCs. The significantly lowered H 2 kinetic order confirms the increased surface H* coverage in this inverse configuration. Decoupling the strong substrate adsorption sites and hydrogenation sites, the inverse configuration prevents self‐poisoning, enabling complete hydrogenation using crude H 2 and solvent‐free LOHCs. This work highlights the superior substrate generality and complete‐hydrogenation capability of the Ni inverse catalyst, establishing such inverse systems as a versatile platform for mild and robust LOHC‐based hydrogen storage.