Proton Hopping-Induced Ring-Opening Hydrogenation of Furfural into 1,5-Pentanediol over Co/CoFe LDHs via Surface Proton Cycling

Although metal/hydroxide catalysts overcome the seesaw effect that limits the performance of conventional metal/oxides in converting furfural to 1,5-pentanediol, their high-temperature synthesis restricts the selection of hydroxides, accompanied by a vague catalytic mechanism of hydroxides in the reaction. Herein, the well-defined Co/CoFe LDHs catalyst is designed with a universal sodium borohydride reduction strategy, which achieves a remarkable productivity over 64 mmol·g–1·h–1. Combined H/D exchange experimental results, theoretical calculations, and isotopic kinetic studies reveal that Co/CoFe LDHs facilitate the ring-opening hydrogenation of furfuryl alcohol to 1,5-pentanediol mediated via a proton hopping mechanism, wherein proton-coupled electron transfer (PCET) occurs through dynamic interface reconstruction and is driven by temperature and H2 pressure. Also, the introduction of oxyphilic Fe modulates the interfacial electronic environment, enhancing substrate adsorption, suppressing side reactions, and facilitating surface protonation. This work uncovers the ring-opening mechanism over metal/hydroxides catalysts and contributes to the rational design of efficient hydrogenation catalysts.