Low-Temperature Selective Oxidative Dehydrogenation of Cyclohexene by Titania-Supported Nanostructured Pd, Pt, and
Mykhailo Vaidulych1, Li-Ya Yeh2, Robin Hoehner2
1Department of Nanocatalysis, J. Heyrovský Institute of Physical Chemistry, v.v.i., Czech Academy of Sciences, Dolejškova 2155/3, CZ-182 23 Prague 8, Czech Republic.
Abstract:
Films of titania-supported monometallic Pd, Pt, and bimetallic Pt-Pd catalysts made of metallic nanoparticles were prepared by magnetron sputtering and studied in the oxidative dehydrogenation (ODH) of cyclohexene. Pd/TiO and Pt-Pd/TiO were found active at as low temperature as 150 °C and showed high catalytic activity with high conversion (up to 81%) and benzene selectivity exceeding 97% above 200 °C. In turn, the Pt/TiO catalyst performed poorly with the onset of benzene production at 200 °C only and conversions not exceeding 5%. The activity of bimetallic Pt-Pd catalysts far exceeded all of the other investigated catalysts at temperatures below 250 °C. However, the production of benzene significantly dropped with a further temperature increase due to the enhanced combustion of CO2 at the expense of benzene formation. As in situ NAP-XPS measurement of the Pt-Pd/TiO catalyst in the reaction conditions of the ODH of cyclohexene revealed Pd surface enrichment during the first temperature ramp, we assume that Pd surface enrichment is responsible for enhanced activity at low temperatures in the bimetallic catalyst. At the same time, the Pt constituent contributes to stronger cyclohexene adsorption and oxygen activation at elevated temperatures, leading to changes in conversion and selectivity with a drop in benzene formation and increased combustion to CO2. Both the monometallic Pd and the Pt-Pd-based catalysts produced a small amount of the second valuable product, cyclohexadiene, and below 250 °C produced only a negligible amount of CO2 (<0.2%). To summarize, Pd- and Pt-Pd-based catalysts were found to be promising candidates for highly selective low-temperature dehydrogenation of cyclic hydrocarbons that showcased reproducibility and stability after the temperature activation. Importantly, these catalysts were fabricated by utilizing proven methods suitable for large-scale production on extended surfaces.
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