Proton Hopping-Induced Ring-Opening Hydrogenation of Furfural into 1,5-Pentanediol over Co/CoFe LDHs via Surface Proton Cycling
Yongwang Li, Ming-Shuai Sun, Botao Wu, Fumin Wang, Xubin Zhang, Zheng Wang, Jiaxing Zhang, Guilin Liu, Junqi Zhang, Kai-Hao Li
Abstract
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 H 2 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.