title: Synthesis of 2-Butanol by Selective Hydrogenolysis of 1,4-Anhydroerythritol over Molybdenum Oxide-Modified Rhodium-Supported Silica.
abstract: Rh-MoOx /SiO2 (Mo/Rh=0.13) is an effective catalyst for the hydrogenolysis of 1,4-anhydroerythritol (1,4-AHERY) and provides 2-BuOH in high yield of 51 %. This is the first report of the production of 2-BuOH from 1,4-AHERY by hydrogenolysis. 1,4-AHERY was more suitable as a starting material than erythritol because the 2-BuOH yield from erythritol was low (34 %). Based on the kinetics and comparison of reactivities of the related compounds using Rh-MoOx /SiO2 and Rh/SiO2 catalysts, the modification of Rh/SiO2 with MoOx leads to the high activity and high selectivity to 2-BuOH because of the generation of reactive hydride species and the strong adsorption of 1,4-AHERY on MoOx species. The reaction proceeds by main two routes, (I) the combination of single C-O hydrogenolysis with the desorption of intermediates, a usual route in hydrogenolysis, and (II) multiple C-O hydrogenolysis without the desorption of intermediates from the active site, and the reaction mechanism for Route (II) is proposed.
authors.affiliation: Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Arai
authors.affiliation: Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan.|Research Center for Rare Metal and Green Innovation, Tohoku University, 468-1, Aoba, Aramaki, Aoba-ku, Sendai, 980-0845, Japan.
authors.forename: Masazumi
authors.initials: M
authors.lastname: Tamura
authors.affiliation: Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan.|Research Center for Rare Metal and Green Innovation, Tohoku University, 468-1, Aoba, Aramaki, Aoba-ku, Sendai, 980-0845, Japan.
authors.forename: Yoshinao
authors.initials: Y
authors.lastname: Nakagawa
authors.affiliation: Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan. tomi@erec.che.tohoku.ac.jp.|Research Center for Rare Metal and Green Innovation, Tohoku University, 468-1, Aoba, Aramaki, Aoba-ku, Sendai, 980-0845, Japan. tomi@erec.che.tohoku.ac.jp.
authors.forename: Keiichi
authors.initials: K
authors.lastname: Tomishige
mesh_terms: D000440:Butanols / Q000138:chemical synthesis* / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D004896:Erythritol / Q000031:analogs & derivatives* / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D007700:Kinetics; D008982:Molybdenum / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*
chemical_list: C518865:1,4-anhydroerythritol; D000440:Butanols; D010087:Oxides; C043958:2-butanol; D012822:Silicon Dioxide; D006859:Hydrogen; D008982:Molybdenum; D012238:Rhodium; D004896:Erythritol
keywords: alcohols; biomass; heterogeneous catalysis; rhodium; supported catalysts