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<p>Full exploitation of shale resources requires new catalytic techniques to efficiently convert the methane, ethane, and propane found in shale gas to value-added fuels and chemicals. A promising process of converting ethane and propane involves catalytic light alkane dehydrogenation and the subsequent oligomerization of light alkenes. The first part of this work focuses on the examination of the mechanistic details of propane dehydrogenation on Pt-based alloy catalysts, where first principles-based free energy, microkinetic, and degrees of rate control analyses are performed to understand and rationalize the selective propane dehydrogenation using a Pt3Mn alloy. We show that only the under-coordinated, Mn-decorated Pt sites, represented by a Pt3Mn(211) surface, are selective to propylene formation, which can be attributed to several key mechanistic details: (1) facile propylene desorption and (2) hindered pathways that are inherently non-selective to propylene and lead to the formation of isomers. These kinetic details can, in turn, be interpreted using the free energy landscapes of propane dehydrogenation on the Pt3Mn(211) surface, which features a reasonably stronger binding of propylene than those of its isomers. From this study, we extract two selectivity descriptors for propane dehydrogenation: The energetics of propylene desorption versus deep-dehydrogenation, as well as the energetics of the formation of propylene versus its isomers. The properties can be used for designing further improved light alkane dehydrogenation catalysts.</p>
| Identifer | oai:union.ndltd.org:purdue.edu/oai:figshare.com:article/20755381 |
| Date | 04 October 2022 |
| Creators | Yinan Xu (12877394) |
| Source Sets | Purdue University |
| Detected Language | English |
| Type | Text, Thesis |
| Rights | CC BY 4.0 |
| Relation | https://figshare.com/articles/thesis/First_Principles_Analysis_of_Catalytic_Conversion_of_Light_Alkanes_to_Value-added_Fuels_and_Chemicals/20755381 |
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