Iodine-Modified Pd Catalysts Promote the Bifunctional Catalytic Synthesis of 2,5-Hexanedione from C₆ Furan Aldehydes

Currently, low intimacy between hydrogenation sites and acidic sites causes unsatisfactory catalytic activity and selectivity for the synthesis of 2,5-hexanedione from C₆ furan aldehydes (5-methylfurfural, 5-hydroxymethylfurfural). Herein, iodine(I) modification of Pd-supported catalysts (such as PdI/Al₂ O₃ and PdI/SiO₂ ) was investigated to modulate the hydrogenation sites and acidic sites. Unlike Pd catalysts that produced 71.4 % yield of 2-hydroxymethyl-5-methyl tetrahydrofuran via an overhydrogenation route of 5-methylfurfural, PdI catalysts showed a high efficiency for 2,5-hexanedione with 93.7 % yield by a hydrogenative ring-opening route. More importantly, the selective synthesis of 2,5-hexanedione from 5-hydroxymethylfurfural with a high yield of 50.2 % by the hydrogenolysis and subsequent ring-opening route was reported for the first time. I-modified Pd nanoparticles produced in-situ hydrogen spillover, which promoted the selective C=O hydrogenation and ring-opening steps by regulating the adsorption configuration of the reactants and the transformation of Lewis to Brønsted acidity, respectively.