Tuning Metal–Acid Cooperativity of Beta Zeolite-Supported Pt Catalysts for Selective Hydrogenolysis of 5-Hydroxymethylfurfural to Methyl Levulinate

Abstract The selective hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) to methyl levulinate (ML) is challenging due to competing side reactions and the instability of conventional metal–acid bifunctional catalysts. Herein, we report the first demonstration of beta zeolite-supported Pt catalysts (Pt/BEA) that enable highly selective conversion of HMF to ML through precise control of framework composition, acidity, and metal–support interactions. Systematic tuning of the Si/Al ratio and Pt loading reveals that framework Al is essential for generating Brønsted acidity and stabilizing active Pt species within a Lewis-acidic environment. Pyridine-Fourier-transform infrared analysis identifies 0.5Pt/BEA-12.5 as the optimal catalyst, exhibiting a balanced Brønsted/Lewis acidity where Lewis sites activate carbonyl intermediates while moderated Brønsted acidity promotes esterification without excessive humin formation. Structural and electronic characterizations confirm the synergistic coexistence of metallic Pt0 and electrophilic Ptδ+ species, facilitating efficient H2 dissociation and selective hydrogenolysis pathways. Under optimized conditions, >99% HMF conversion with 92.0% ML yield is achieved at low Pt loading. Importantly, the catalyst also demonstrates effective ML production from real sugar feedstocks (glucose, fructose, and sucrose), highlighting its practical applicability and sustainability for biomass upgrading to fuel additives and value-added chemicals.