title: C-O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites.
abstract: We studied the C-O cleavage of phenolate and catecholate at step sites of a Ru catalyst using periodic DFT methods at the GGA level. Both C-O scission steps are associated with activation barriers of about 75 kJ mol(-1), hence are significantly more facile than the analogous reactions on Ru terraces. With these computational results, we offer an interpretation of recent experiments on the hydrodeoxygenation of guaiacol (2-methoxyphenol) over Ru/C. We hypothesize that the experimentally observed dependency of the product selectivity on the H2 pressure is related to the availability of step sites on a Ru catalyst.
authors.affiliation: Institute of High Performance Computing, Agency for Science, Technology and Research, 1 Fusionopolis Way, #16-16 Connexis, Singapore 138632, Singapore.
authors.forename: Cheng-chau
authors.initials: CC
authors.lastname: Chiu
authors.forename: Alexander
authors.initials: A
authors.lastname: Genest
authors.forename: Armando
authors.initials: A
authors.lastname: Borgna
authors.forename: Notker
authors.initials: N
authors.lastname: Rösch
mesh_terms: D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D002396:Catechols / Q000737:chemistry*; D006139:Guaiacol / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D062385:Hydroxybenzoates / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D002396:Catechols; D062385:Hydroxybenzoates; D006139:Guaiacol; D002244:Carbon; D012428:Ruthenium; D006859:Hydrogen; C017616:phenolic acid; C034221:catechol; D010100:Oxygen