Interfacial Engineering of Ni Domain with Alumina Ensembles to Enhance Coke-Resistance for Durable Hydrogenolysis

Owing to its unique multifunctionality, Ni has been extensively employed in diverse catalytic systems; however, its performance is severely constrained by pronounced coking that results in rapid catalyst deactivation. Herein, we report a strategy for enhancing coke resistance of Ni-based catalyst by surface modification with interfacial AlOx. Specifically, AlOx ensembles were constructed on supported Ni nanoparticles by high-temperature reduction, generating abundant Ni-Al interfaces. This strengthens Ni-Al electronic interactions and decreases the electron density of Ni domains, thereby attenuating the surface basicity. In tandem aqueous-phase reforming (APR, for hydrogen generation) and C-O bond hydrogenolysis (for depolymerization of etheric aromatics), this tailored surface property substantially raises the energy barrier for aldol condensation of APR intermediates—a key undesired side reaction responsible for carbon-chain growth. Consequently, carbonaceous deposition is suppressed, enabling durable tandem APR-hydrogenolysis. In contrast to bare Ni nanoparticles that undergo near-complete deactivation within six cycles, the AlOx-modified Ni sustains stable APRhydrogenolysis performance. This work provides an interface-engineering strategy to enhance the coke resistance while preserving the essential functionalities of the catalysts.