Cu–MgO interfacial electronic interactions promote selective ring-opening hydrogenolysis of furfuryl alcohol to 1,2-pentanediol

EMSI enhances FFA ring-opening hydrogenolysis to 1,2-PeD. • Electron-deficient Cu species and basic sites synergistically activate C–O bonds. • In situ ATR-FTIR reveals furan-ring opening and C 5 intermediate formation. • DFT reveals furan-O adsorption promotes C 5 –O 1 bond polarization and cleavage. Selective hydrogenolysis of furfuryl alcohol (FFA) to 1,2-pentanediol (1,2-PeD) offers a route for biomass valorization. However, catalysts suffer from unclear active-site configurations and insufficient activation of the key C–O bond. To address this, a Cu/MgO catalyst featuring basic sites and electron-deficient Cu active sites at the interface is developed. Compared with Cu/Al 2 O 3 and Cu/CeO 2 , Cu/MgO achieves 97% FFA conversion and 45% 1,2-PeD selectivity under continuous-flow conditions at 140 °C and 6 MPa H 2 . In situ XPS, in situ ATR-FTIR, and DFT calculations indicate that electronic metal-support interaction (EMSI) at the Cu–MgO interface induces interfacial charge redistribution and favors ring-opening hydrogenolysis. The resulting electron-deficient Cu species and MgO-derived basic sites cooperatively promote FFA adsorption through the furan-ring oxygen, C–O bond activation, C 5 carbonyl intermediate formation, and hydrogenation to 1,2-PeD. This work addresses the mechanistic gap between EMSI and the ring-opening hydrogenolysis of FFA over Cu–MgO catalysts. Cu–MgO interfacial sites, where EMSI generates electron-deficient Cu species while MgO provides basic sites, enable selective ring-opening hydrogenolysis of furfuryl alcohol to 1,2-pentanediol. Preferential adsorption through the furan-ring O atom positions the C 5 –O 1 bond near the Cu–MgO interface, promoting interfacial polarization, selective C–O bond cleavage, C 5 carbonyl intermediate formation, and subsequent hydrogenation to 1,2-pentanediol, as supported by in situ XPS, in situ ATR-FTIR, and DFT calculations. Download: Download high-res image (331KB) Download: Download full-size image