La2CuO4 decorated inverse-phase Cu catalysts for highly selective ring-opening hydrogenolysis of furfuryl alcohol to 1,2-pentanediol

La 2 CuO 4 decorated inverse Cu catalysts enable selective FFA hydrogenolysis. • 10La/Cu delivers a 72.8% yield of 1,2-pentanediol from furfuryl alcohol. • Cu + –O v –La 3+ sites enable η 2 -(O, O)-FFA dual-site adsorption. • Cu 0 and Cu + –O v –La 3+ sites synergistically promote FFA adsorption and C 5 O cleavage. • 10La/Cu maintains stable performance for 200 h in a continuous flow fix-bed reactor. Selective conversion of furanic compounds to alkyl diols via furan ring-opening hydrogenolysis is of great importance for biomass refining, but remains challenging due to the inherent inertness of C−O−C bonds. In this work, an inverse-phase Cu catalyst decorated with La 2 CuO 4 domains was developed for the ring-opening hydrogenolysis of furfuryl alcohol (FFA) to 1,2-pentanediol (1,2-PeD). The optimized 10La/Cu catalyst afforded a 72.8% yield of 1,2-PeD at 140 °C under 6 MPa H 2 , which represents one of the best catalytic performance among previously reported Cu-based catalysts. Extensive characterization revealed that the intimate interaction between La 2 CuO 4 and metallic Cu generated abundant interfacial sites. Upon reduction, hydrogen spillover from metallic Cu to adjacent La 2 CuO 4 promoted the formation of an oxygen-vacant La 2 CuO 4 phase that are enriched with Cu + −O v −La 3+ sites. EXAFS analysis indicated that the Cu + −O v −La 3+ sites possess a Cu−La spatial distance of 0.32 nm, which well matches the atomic distance of two oxygen atoms in FFA molecules. In-situ FTIR and model reactions suggested that the formation of an η 2 -(O, O)-FFA dual-adsorption configuration on Cu + −O v −La 3+ sites may facilitate the selective activation of C−O−C bonds. Meanwhile, the sterically less hindered C 5 −O bond of the activated furan ring is selectively hydrogenolyzed by metallic Cu sites to form 1,2-PeD. This study provides mechanistic insight into selective furan ring hydrogenolysis and offers a feasible non-noble-metal-based catalyst with promising potential for practical application for the conversion of FFA to 1,2-PeD. Download: Download high-res image (265KB) Download: Download full-size image