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

Abstract Currently, low intimacy between hydrogenation sites and acidic sites causes unsatisfactory catalytic activity and selectivity for the synthesis of 2,5‐hexanedione from C 6 furan aldehydes (5‐methylfurfural, 5‐hydroxymethylfurfural). Herein, iodine(I) modification of Pd‐supported catalysts (such as PdI/Al 2 O 3 and PdI/SiO 2 ) 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.