Formation of CO2 and Ethane from Propionyl over Platinum: A Density Functional Theory Study

The conversion of propionyl, the most stable dehydrogenation product of 1-propanol on flat and stepped Pt(111) surfaces is explored computationally as a model for the transformation of alcohols on Pt to CO2 and hydrocarbons. We studied a reaction network in which dehydrogenation steps or hydroxyl insertion may precede the desired C-C cleavage, via either decarboxylation or decarbonylation. In the latter case, CO2 will be obtained via a subsequent water-gas-shift reaction. On a flat surface, the decarbonylation pathway with the highest barrier of 91 kJ mol(-1) was calculated to be preferred, as the decarboxylation reactions are inaccessible because of high barriers of the preceding dehydrogenations, 129 kJ mol(-1), or the C-C bond scission itself, 204 kJ mol(-1). At step defects the highest barrier for decarboxylation was determined to be notably lower, at 86 kJ mol(-1), making this pathway competitive for C-C scission.     «

The conversion of propionyl, the most stable dehydrogenation product of 1-propanol on flat and stepped Pt(111) surfaces is explored computationally as a model for the transformation of alcohols on Pt to CO2 and hydrocarbons. We studied a reaction network in which dehydrogenation steps or hydroxyl insertion may precede the desired C-C cleavage, via either decarboxylation or decarbonylation. In the latter case, CO2 will be obtained via a subsequent water-gas-shift reaction. On a flat surface, the...     »

ISI Document Delivery No.: 197LO Times Cited: 0 Cited Reference Count: 75 Basaran, Duygu Genest, Alexander Lercher, Johannes A. Roesch, Notker European Graduate School of Sustainable Energy Technologies; Fonds der Chemischen Industrie (Germany) We thank Cheng-chau Chiu and Zhi-Jian Zhao for helpful discussions. D.B. is grateful for a fellowship of the European Graduate School of Sustainable Energy Technologies. This work was supported by Fonds der Chemischen Industrie (Germany) and generous computing resources at Leibniz Rechenzentrum Munchen. 0 Amer chemical soc Washington     «

ISI Document Delivery No.: 197LO Times Cited: 0 Cited Reference Count: 75 Basaran, Duygu Genest, Alexander Lercher, Johannes A. Roesch, Notker European Graduate School of Sustainable Energy Technologies; Fonds der Chemischen Industrie (Germany) We thank Cheng-chau Chiu and Zhi-Jian Zhao for helpful discussions. D.B. is grateful for a fellowship of the European Graduate School of Sustainable Energy Technologies. This work was supported by Fonds der Chemischen Industrie (Germany) and generous com...     »