Cu-MOF-derived Cu/C catalysts via solvent polarity engineering with renewable ligand for efficient hydrogenation of levulinic acid to γ-valerolactone

The synthesis of value-added chemicals from renewable biomass is becoming increasingly important in the transition to a sustainable and low-carbon energy system. Herein, we demonstrate a solvent-polarity modulation strategy to engineer biomass-derived Cu-MOF using 2,5-furandicarboxylic acid (FDCA) as a renewable ligand, where tailored β/α ratios via Kamlet-Taft parameters balance nucleation-growth kinetics to optimize textural properties. Pyrolyzed Cu-MOF at 500 °C under a nitrogen atmosphere yield the Cu/C catalysts, which were subsequently employed in the selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). Among the various solvents used, the Cu-MOF precursor synthesized in a mixed solvent of methanol and N, N-dimethylformamide (DMF) demonstrated the highest catalytic performance, outperforming those synthesized in other solvents. This highlights the significant impact of solvent selection on the structure of Cu-MOF, which in turn affects their hydrogenation activity. Advanced characterization confirming that the uniform Cu dispersion (confirmed by HRTEM mapping) and Cu⁰/Cu⁺ electronic synergy (via Cu Auger analysis) enhanced hydrogenation performance. Additionally, the biomass-derived catalysts exhibited excellent durability. Overall, this research provides a promising approach to develop highly efficient catalysts using renewable ligands and demonstrates the potential of regulating catalyst properties through the strategic selection of solvents, as informed by Kamlet-Taft parameters. Utilizing renewable FDCA ligands, solvent polarity engineering (guided by Kamlet-Taft parameters β/α) regulates Cu-MOF assembly, followed by pyrolysis to construct the Cu/C catalysts. Synergistic Cu⁰-Cu⁺ interfaces and well-dispersed Cu species on Cu/C-DM catalysts drive excellent catalytic performance on hydrogenation of Levulinic Acid (LA) to γ-Valerolactone (GVL). • Biomass-Cu-MOF via β/α-tuned Kamlet-Taft solvents balances nucleation-growth kinetics for high surface area/morphology. • Cu/C-DM achieves 100 % LA conv. and 98.8 % GVL yield with stable aqueous hydrogenation (130 °C, 3 MPa H₂, 6 h). • High-dispersion Cu NPs (geometric) and Cu⁰/Cu⁺ pairing (electronic) synergistically boost catalysis. • Biomass ligands and solvent engineering provide a green route for designing efficient MOF-derived catalysts.