Understanding the Role of Base Species on Reversed Cu Catalyst in Ring Opening of Furan Compounds to 1, 2‐Pentanediol

Abstract The hydrogenation of biomass‐derived furan compounds provides a sustainable pathway for the production of various valuable chemicals; product selectivity among multiple reaction pathways of furan compound hydrogenation is crucially dependent on catalytic sites; however controlling reaction pathways remains challenging due to the lack of identification and understanding of active sites. In this work we reveal the role of base sites in furfural selective hydrogenation through deliberately designed and synthesized reversed catalysts, basic metal oxides and hydroxide on Cu. It is demonstrated that base species greatly enhanced the selectivity of 1, 2‐pentanediol (1, 2‐PeD) from furfural, presenting a nearly fourfold increase of 1, 2‐PeD: methyl furan ratio over the Cu based reverse catalysts. A combination of infrared spectroscopy and DFT calculations demonstrates the strong interaction between the C−O−C bond in furan ring and the catalyst surface in preferentially parallel adsorption mode in the presence of base species on Cu, thus facilitating the activation of C−O−C bond to produce 1, 2‐PeD. This work provides a strategy of designing reversed catalyst to study the effect of promoters and reveals the role of base sites in the hydrogenation of biomass‐derived furan compounds to diols.