Pt nanoparticles in cooperation with Mn-P composite drive base-free selective oxidation of 5-hydroxymethylfurfural

Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a key approach to sustainable upgrading of furfural based biomass resources. In this work, small Pt nanoparticles (about 2.1 nm) loaded on MnP_nO_x composite were shown to effectively drive the base-free aerobic oxidation of HMF to FDCA in water. Regulating the P content in carrier enabled to tune HMF conversion and product distribution. The optimal Pt/MnP_0.5O_x catalyst can reach 98% yield of FDCA at 110 °C under 10 bar of O₂ after 24 h. It also showed the highest initial conversion rate of HMF (13 mmol mol_Pt⁻¹ s⁻¹) and productivity of FDCA (4.1 mmol mol_Pt⁻¹ h⁻¹) among all the Pt/MnP_nO_x catalysts. The carrier effect of P addition on promoting Pt oxidation catalysis was elucidated by using rigorous kinetic investigations and comprehensive characterizations. The initial conversion rate, rate constant and apparent activation energy were independently measured on oxidation of HMF and its derived intermediates. ICP-MS, XRD, TEM, H₂-TPR, O₂-TPD and XPS were used to acquire catalytic properties. It was demonstrated that P addition led to changes in carrier structure and metal-support interaction, which eventually promoted the formation of highly active electron-rich Pt⁰ sites and mobile reactive defect oxygen species. These features allowed improving the selective oxidation catalysis of supported-Pt nanoparticles for the base-free conversion of HMF to FDCA.