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Ring opening hydrogenolysis of 5-hydroxymethyl furfural over supported bimetallic catalysts
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DOI：10.1039/D5CY01286D.png)
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Abstract
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The selective conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 1; 6-hexanediol (1; 6 HDO) is a promising pathway for sustainable production of chemicals from renewable feedstock. Here; we report the catalytic performance of various supported platinum catalysts; including monometallic Pt nanoparticles on different supports (CeO₂; MgO; hydrotalcite; and hydroxyapatite) and bimetallic (PtPd; PtCo; PtRu; and PtRe) nanoparticles supported on hydroxyapatite for this reaction under batch reaction conditions. Among the monometallic catalysts; Pt supported on hydroxyapatite (Pt/HAP) demonstrated the highest selectivity (30%) for 1; 6 HDO at 85% HMF conversion. This superior performance is attributed to the amphoteric properties of the hydroxyapatite support. Notably; the incorporation of Ru as a second metal in the Pt nanoparticles significantly improved catalytic efficiency. The bimetallic PtRu/HAP catalyst achieved an impressive selectivity of 62% for 1; 6 HDO at 85% conversion. Characterization by X-ray Photoelectron Spectroscopy (XPS) and Electron Microscopy revealed that the addition of Ru to Pt nanoparticles resulted in smaller bimetallic nanoparticle sizes compared to monometallic Pt nanoparticles; contributing to the enhanced 1; 6 HDO selectivity observed for the bimetallic system. The effects of reaction temperature and pressure on 1; 6-hexanediol selectivity were also studied. Additionally; the acidity and basicity of the hydroxyapatite supported catalyst were analysed using the surface Ca/P ratio as well the CO2 and NH3 TPD data. The results show that the PtRu/HAP catalyst has optimal acidic site density and least basic sites compared to the monometallic catalysts. This unique combination of acidic and basic surface properties; together with the synergistic effects of the finely dispersed smaller bimetallic PtRu nanoparticles; makes this material one of the most active catalysts for the selective hydrogenolysis of HMF to 1; 6 HDO
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