caa a22 4500 606174311 CHVBK 20210128100737.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s11244-015-0402-0 doi (NATIONALLICENCE)springer-10.1007/s11244-015-0402-0 A Comparative Study of Methanol Adsorption and Dissociation over WO3(001) and ReO3(001) [Elektronische Daten] [Qingfeng Ge, Maciej Gutowski] Tungsten (5d46s2) and rhenium (5d56s2) form MO3 oxides (M=W or Re) with similar structures. The adsorption and dissociation of methanol on these oxide surfaces, often used to probe the surface redox centers, have been analyzed using periodic density functional calculations. Molecular adsorption of methanol at the metal site on both surfaces with 0.5ML oxygen coverage was found to be exothermic with adsorption energies of −74 and −106kJ/mol on WO3(001) and ReO3(001), respectively. In contrast, heterolytic dissociation of methanol to adsorbed methoxide species at the metal site and H at the surface oxygen site is not energetically favored on WO3(001) but favored on ReO3(001). The dissociation energies to form coadsorbed methoxide and hydrogen adatom are 35kJ/mol on WO3 and −112kJ/mol on ReO3, respectively. The activation barrier for dissociating the molecularly adsorbed methanol on ReO3(001) was determined to be 19kJ/mol. Dehydrogenation to form coadsorbed hydroxymethyl and hydrogen adatom is not energetically favorable on both surfaces with respect to the molecularly adsorbed methanol. However, the dehydrogenation path is exothermic on ReO3 with respect to the gas phase methanol, with the heats of reaction of −25kJ/mol, but highly endothermic on WO3, with the heats of reaction of 114kJ/mol. Springer Science+Business Media New York, 2015 Transition metal oxides nationallicence Methanol nationallicence Dissociation nationallicence Dehydrogenation nationallicence DFT nationallicence Ge Qingfeng Department of Chemistry and Biochemistry, Southern Illinois University, 62901, Carbondale, IL, USA aut Gutowski Maciej Chemical Sciences Division, Fundamental Sciences Directorate, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/10-11(2015-08-01), 655-664 1022-5528 58:10-11<655 2015 58 11244 https://doi.org/10.1007/s11244-015-0402-0 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-015-0402-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ge Qingfeng Department of Chemistry and Biochemistry, Southern Illinois University, 62901, Carbondale, IL, USA aut NATIONALLICENCE 700 1- Gutowski Maciej Chemical Sciences Division, Fundamental Sciences Directorate, Pacific Northwest National Laboratory, P.O. Box 999, 99352, Richland, WA, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/10-11(2015-08-01), 655-664 1022-5528 58:10-11<655 2015 58 11244