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Updated: Oct 16, 2026

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A study on the selectivity in 5-hydroxymethylfurfural reduction using SnO2-decorated Ru catalysts: unveiling the
Adrián García-Zaragoza1, Christian Cerezo-Navarrete1, Carlo Marini2
1ITQ, Instituto de Tecnología Química, Universitat Politècnica de València (UPV), Av. de los Naranjos S/N 46022, Valencia, Spain. chcena@upv.es.
Abstract:
The selective transformation of biomass-derived platform molecules into value-added chemicals requires catalysts capable of controlling the competition between hydrogenation and hydrodeoxygenation (HDO) pathways. Herein, graphene-supported Ru nanoparticles (RuNPs) were modified through a surface organometallic chemistry (SOMC) approach using tributyltin hydride (Bu3SnH), generating surface SnO2 species on the Ru NPs, as supported by XPS and XAS analyses. The catalytic performance of the resulting Ru@rGO/SnO2(x) materials (x = 0.5, 0.8 and 1 equiv.) was investigated in the reduction of 5-hydroxymethylfurfural (HMF). Unmodified Ru@rGO exhibited high hydrogenation activity, achieving 97.9% conversion with 94% selectivity towards 2,5-bis(hydroxymethyl)furan (BHMF) after 3 h and complete conversion to 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) after 20 h. In contrast, the progressive incorporation of SnO2 species modified the product distribution by suppressing the hydrogenation of the aromatic furan ring while promoting HDO. As a result, Ru@rGO/SnO2(1) completely inhibited the formation of hydrogenated furan-ring products, reaching 97.7% selectivity to 2,5-dimethylfuran (DMF) at extended reaction times. Combined adsorption studies, control experiments and computational calculations revealed that HDO processes only occur when the aromaticity of the furan ring is preserved. Once the ring is hydrogenated, the resulting products preferentially adsorb on the graphene support and become inactive towards further hydrodeoxygenation. These findings demonstrate that surface SnO2 species provide an effective strategy to tune the selectivity of Ru NPs and unveil the key role of furan-ring aromaticity in governing hydrodeoxygenation processes of biomass-derived molecules.
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