Switching Reaction Pathways in Erythritol Conversion by Controlling Promoter Reducibility and Metal Proximity in Pt‐Based Catalysts

In this work, monometallic and bimetallic Pt‐based catalysts were synthesized and evaluated in liquid‐phase erythritol C–O hydrogenolysis reactions for butanediol production. The solids were prepared by incipient wetness impregnation and characterized by temperature programmed reduction, NH 3 temperature programmed desorption, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy. Physicochemical analyses revealed a strong influence of metal nature and reducibility on the acidic and electronic properties of the catalysts, which affected their catalytic behavior. The Pt–Re system exhibited higher reducibility and improved spatial distribution between metals. The close proximity of Pt and Re species enhanced hydrogen spillover and facilitated C─O bond cleavage. In contrast, Pt–W and Pt–Mo systems showed weaker metal–metal interaction and higher acid site density associated with poorly reduced species, promoting dehydration pathways. Under the studied reaction conditions ( C ERY = 0.4 M, 473 K, P H2 = 25 bar, C cat = 12.5 g L −1 ), PtRe(1)/TiO 2 reached 75% erythritol conversion after 8 h, being highly selective toward C–O hydrogenolysis, with predominant formation of 1,2‐butanediol and 2,3‐butanediol. Reaction mechanism analysis suggests a synergistic interaction between metallic Pt and partially reduced Re species, favoring the formation of active sites for C─O bond cleavage. These findings highlight that promoter reducibility and Pt‐promoter proximity govern acidity, hydrogenolysis activity, and selectivity providing guidelines for the rational design of efficient bifunctional catalysts for biomass valorization.