Regulating Interfacial Functional Balance via an Entropy-Stabilized Multimetallic PdPtRuCuNi Nanostructure for Selective Cellulose Hydrogenolysis to Ethylene Glycol

Abstract Selective conversion of cellulose into C2 polyols under aqueous-phase conditions remains challenging due to the difficulty in coordinating hydrolysis, C–C bond scission, and hydrogenation while suppressing nonproductive side reactions. Herein, we report an ultrasmall entropy-stabilized multimetallic PdPtRuCuNi nanocatalyst supported on defect-rich nanostructured WOx that enables precise interfacial regulation of the interfacial functional balance. Under relatively mild hydrothermal conditions, the nanocatalyst achieves complete cellulose conversion with a high ethylene glycol selectivity of 65.7%, significantly outperforming the corresponding single-metal nanocatalysts. Spectroscopic and kinetic analyses reveal an exceptionally low apparent activation energy, which originates from the surface-assisted hydrolysis pathway constructed by the nanoscale metal-oxide contact interface with superior interfacial wettability and abundant oxygen vacancies at the nanointerface. Mechanistic studies demonstrate that the electronically coupled multimetallic sites provide an ultrahigh hydrogenation rate that effectively traps reactive C2 fragments before they undergo rearrangement to organic acids. This work identifies rational modulation of nanoscale interfacial functional balance as a universal design principle to boost target product selectivity and carbon utilization efficiency for aqueous-phase biomass catalytic conversion.