Akpe, Shedrack G. Choi, Sun Hee Ham, Hyung Chul 2024-01-19T13:03:17Z 2024-01-19T13:03:17Z 2022-01-10 2021-12-01 1463-9076 https://pubs.kist.re.kr/handle/201004/115946 There is currently no theoretical study on the hydrogenation of xylose to xylitol on a catalyst's surface, limiting proper understanding of the reaction mechanisms and the design of effective catalysts. In this study, DFT techniques were used for the first time to investigate the mechanisms of xylose to xylitol conversion on five notable transition metal (TM) surfaces: Ru(0001), Pt(111), Pd(111), Rh(111), and Ni(111). Two transition state (TS) paths were investigated: TS Path A and TS Path B. The TS Path B, which was further subdivided into TS Path B1 and B2, was proposed to be the minimum energy path (MEP) for the reaction process. According to our computational results, the MEP for this reaction begins with the structural rearrangement of cyclic xylose into its acyclic form prior to step-wise hydrogenation. The rate-determining step (RDS) on Ru(0001), Pt(111), Pd(111), and Ni(111) was discovered to be the ring-opening process via C-O bond scission of cyclic xylose. On Rh(111), however, the RDS was found to be the first hydrogenation stage, leading to the hydrogenation intermediate. Furthermore, based on the RDS barrier, our results revealed that the activities of the tested TM surfaces follow the trend: Ru(0001) > Rh(111) >= Ni(111) > Pd(111) > Pt(111). This result demonstrates the higher activity of Ru(0001) compared to other surfaces used for xylose hydrogenation. It correlates with experimental trends in relation to Ru(0001) superiority and provides the basis for understanding the theoretical design of economical and more active catalysts for xylitol production. English ROYAL SOC CHEMISTRY FORMIC-ACID DECOMPOSITION HCOOH DECOMPOSITION FURFURYL ALCOHOL HYDROGENATION BIOMASS ADSORPTION SURFACE DFT HYDROGENOLYSIS PT(111) Conversion of cyclic xylose into xylitol on Ru, Pt, Pd, Ni, and Rh catalysts: a density functional theory study Article 10.1039/d1cp04660h 1 PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.23, no.46, pp.26195 - 26208 PHYSICAL CHEMISTRY CHEMICAL PHYSICS 23 46 26195 26208 scie scopus 000721519100001 2-s2.0-85120736739 Chemistry, Physical Physics, Atomic, Molecular & Chemical Chemistry Physics Article FORMIC-ACID DECOMPOSITION HCOOH DECOMPOSITION FURFURYL ALCOHOL HYDROGENATION BIOMASS ADSORPTION SURFACE DFT HYDROGENOLYSIS PT(111) biomass bond cleavage catalyst DTF hydrogenolysis hydrogen xylose xylitol proximity energy