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EPR Monitored Redox Titration of the Cofactors of Saccharomyces cerevisiae Nar1
Published on: November 26, 2014
Switching Reaction Pathways in Erythritol Conversion by Controlling Promoter Reducibility and Metal Proximity in
Ludmila N Chorvat1, María E Sad1, Cristina L Padró1
1Catalysis Science and Engineering Research Group (GICIC), Instituto de Investigaciones en Catálisis y Petroquímica-INCAPE-(UNL-CONICET), CCT Santa Fe, Santa Fe, Argentina.
Abstract:
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, NH3 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 (CERY = 0.4 M, 473 K, PH2 = 25 bar, Ccat = 12.5 g L-1), PtRe(1)/TiO2 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.
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