Engineering Inverse Oxide–Metal Interfaces of ZrO2/Cu for Selective Ring-Opening Hydrogenolysis of 5-Hydroxymethylfurfural to Linear Hexanepolyols

Abstract Selective ring-opening hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) offers a sustainable route to linear polyols, but achieving high selectivity remains challenging because of competing hydrogenation pathways and the limited understanding of how catalyst interfaces govern furanic C–O bond activation. Herein, we report an inverse ZrO2/Cu catalyst that enables highly selective conversion of HMF to linear alcohols. The optimized 5ZrO2/Cu catalyst affords an 86.53% yield of linear hexanepolyols at complete HMF conversion, exhibiting a ring-opening rate 4.23 times higher than that of the conventional 95ZrO2/Cu catalyst. Structural characterization reveals that the inverse architecture generates an extended Cu–O–Zr interfacial perimeter and abundant medium-strength basic sites. Kinetic studies show that the inverse catalyst significantly lowers the apparent activation energy for the hydrogenolysis of the key intermediate 2,5-bis(hydroxymethyl)furan. Combined in situ DRIFTS measurements and density functional theory calculations demonstrate that strong interfacial electronic interactions regulate the adsorption geometry of HMF-derived intermediates. Specifically, adsorption through hydroxymethyl groups on interfacial ZrOx sites induces a tilted configuration that weakens the furanic C–O bond and promotes selective ring opening. This work establishes a direct relationship between interfacial electronic structure, adsorption geometry, and reaction selectivity, providing mechanistic insights and a general strategy for designing interface-engineered catalysts for biomass valorization.