Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM₂/NC, TM= Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir₂/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM₂/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.