caa a22 4500 60617429X CHVBK 20210128100737.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s11244-015-0403-z doi (NATIONALLICENCE)springer-10.1007/s11244-015-0403-z CH3CH2OH, CD3CD2OD, and CF3CH2OH Decomposition on ZnO $$ \left( {1\bar{1}00} \right) $$ 1 1 ¯ 00 [Elektronische Daten] [Aaron Reinicker, James Miller, Wooseok Kim, Kijung Yong, Andrew Gellman] The decomposition of CH3CH2OH, CD3CD2OD, and CF3CH2OH on Zn $$ \left( {1\bar{1}00} \right) $$ 1 1 ¯ 00 was studied using temperature programmed reaction spectroscopy. CH3CH=O (CD3CD=O, CF3CH=O), CH2=CH2 (CD2=CD2, CF2=CH2), H2O (D2O) and H2 (D2) were formed in all cases. The CH3CH2OH decomposition mechanism includes the formation of two intermediate species on the surface: CH3CH2- bonded to surface lattice O atoms decomposes to form CH2=CH2 while CH3CH2O- bonded to surface Zn atoms decomposes to form CH3CH=O. A significant isotope effect observed for the formation of CH2=CH2 versus CD2=CD2 suggests that C-H(D) bond breaking at the β-carbon is the rate-limiting step in CH3CH2- (CD3CD2-) decomposition. Decomposition of CF3CH2OH leaves F-atoms on the surface as a result of β-fluoride elimination in CF3CH2-. A significant F substituent effect in desorption of CF3CH=O versus CH3CH=O indicates that the CF3 group increases the barrier to the β-hydride elimination step yielding CF3CH=O and suggests that the transition state is cationic, $$ C^{\delta + } \cdots H^{\delta - } $$ C δ + ⋯ H δ - . Springer Science+Business Media New York, 2015 ZnO nationallicence Ethanol nationallicence Temperature progress nationallicence Reaction spectroscopy nationallicence Kinetic isotope effect nationallicence Substituent effect nationallicence Reinicker Aaron Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut Miller James Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut Kim Wooseok Department of Chemical Engineering, Pohang University of Science and Technology, Gyeongsangbuk-do, South Korea aut Yong Kijung Department of Chemical Engineering, Pohang University of Science and Technology, Gyeongsangbuk-do, South Korea aut Gellman Andrew Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/10-11(2015-08-01), 613-622 1022-5528 58:10-11<613 2015 58 11244 https://doi.org/10.1007/s11244-015-0403-z 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/s11244-015-0403-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Reinicker Aaron Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut NATIONALLICENCE 700 1- Miller James Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut NATIONALLICENCE 700 1- Kim Wooseok Department of Chemical Engineering, Pohang University of Science and Technology, Gyeongsangbuk-do, South Korea aut NATIONALLICENCE 700 1- Yong Kijung Department of Chemical Engineering, Pohang University of Science and Technology, Gyeongsangbuk-do, South Korea aut NATIONALLICENCE 700 1- Gellman Andrew Department of Chemical Engineering, Carnegie Mellon University, 15213, Pittsburgh, PA, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/10-11(2015-08-01), 613-622 1022-5528 58:10-11<613 2015 58 11244