Mechanistic Insights into Catalytic Ethanol Steam Reforming Using Isotope-Labeled Reactants

The low‐temperature ethanol steam reforming (ESR) reaction mechanism over a supported Rh/Pt catalyst has been investigated using isotope‐labeled EtOH and H2O. Through strategic isotope labeling, all nonhydrogen atoms were distinct from one another, and allowed an unprecedented level of understanding of the dominant reaction pathways. All combinations of isotope‐ and non‐isotope‐labeled atoms were detected in the products, thus there are multiple pathways involved in H2, CO, CO2, CH4, C2H4, and C2H6 product formation. Both the recombination of C species on the surface of the catalyst and preservation of the C−C bond within ethanol are responsible for C2 product formation. Ethylene is not detected until conversion drops below 100 % at t=1.25 h. Also, quantitatively, 57 % of the observed ethylene is formed directly through ethanol dehydration. Finally there is clear evidence to show that oxygen in the SiO2‐ZrO2 support constitutes 10 % of the CO formed during the reaction. The tracking of atoms from reactants to products during Rh/Pt catalytic ethanol steam reforming using H312C13CH216OH and H218O provided new insight into the overall reaction mechanism. All combinations of isotope‐ and non‐isotope‐labeled atoms were detected in the products, thus there are multiple pathways involved in H2, CO, CO2, CH4, C2H4, and C2H6 product formation.