Insight into the synergistic enhancement of acidic sites in Co-based catalysts for catalytic production of 1,5-pentanediol by furfuryl alcohol hydrogenation

1,5-pentanediol (1,5-PDO) is a valuable petrochemical for producing advanced polyester and polyurethane. The production of bio-1,5-PDO through hydrogenolysis ring-opening of biomass-derived furfuryl alcohol, is an atom-economical and sustainable alternative to reduce the reliance on fossil energy. Acidic metal oxide was always an component in typical non-noble metal catalysts, but the role of acidic sites on support during the precise cleavage of C–O–C bond in furan ring has been overlooked. Herein, a series of model catalysts were synthesized through metal-organic frameworks, designing highly dispersed Al 2 O 3 -modified Co-based model active sites supported on carbon. The modulation of model active sites are favorable to investigate the synergy mechanism of hydrogenation sites and acidic sites originated from metal oxide support in multicomponent transition metal catalyst. Compared with the catalyst without Al 2 O 3 , the optimized 7AlCo@C-500 catalyst could achieve 98.4 % conversion of FFA and 52.5 % selectivity for 1,5-PDO at 160 °C within 3h, exhibiting comparable performance to the typical transition metal catalysts. Based on the characterization, the Al 2 O 3 in Co-based catalyst results in electron transfer through Co–O–Al interaction, forming more oxygen vacancies in CoOx, and offering weak acidic sites, which facilitated the adsorption of FFA and promoted hydrogenolysis efficiency. Besides, the synergetic effect between Co species and Al 2 O 3 promotes hydrogen dissociation and activation of furan ring in FFA, thereby decreasing the activation energy for hydrogenolysis of FFA. Other acidic metal oxide could exhibit similar promotional effect as Al 2 O 3 , fostering the formation of 1,5-PDO. This study investigates the assistant effects of acidic sites in metal oxide by designing model catalysts, aiming to elucidate the role of acidic metal oxides in transition metal catalyst during the selective conversion of biomass-derived FFA to high-value 1,5-PDO.