Oxidative Coupling of Methane: descriptors for activity and selectivity
Gaurav Kumar, Sai Lap Jacky Lau and Michael J. Janik*
Department of Chemical Engineering, Pennsylvania State University, University Park, PA
Increasing natural gas reserves in the recent years motivate further development of processes to convert methane into value-added products. Since the initial description [1] of catalytic oxidative coupling of methane (OCM) to form C2 hydrocarbons, various pure/doped metal-oxide catalysts have been examined for their methane conversion and C2 selectivity. This ongoing search to find high performing catalysts has been pre-dominantly empirical, and the relationship between active site properties and catalyst activity and selectivity remains unclear. A known dependence of the OCM activity and selectivity on material property(s) enables us to tune active site properties to optimize catalyst performance.
This study uses density functional theory (DFT) methods and the established OCM reaction mechanism [2] to relate activity and selectivity to the surface electronic and structural properties of the catalyst. C-H activation and °¤CH3 radical adsorption determine the activity and selectivity of a catalyst, respectively. Since both of these elementary processes reduce the catalyst surface, we hypothesize that the activity (measured by C-H activation) and selectivity (measured by °¤CH3 adsorption) of the catalyst correlate with surface reducibility. C-H activation energy and °¤CH3 adsorption energy have been plotted against the oxygen vacancy formation energy ¥ÄEvac of various metal-doped CeO2, doped MgO, doped TiO2, ZnO and TbOx. Computational results (Figure 1) show a linear relation of the vacancy formation energy (surface reducibility), with the C-H activation energy and °¤CH3 adsorption energy.
Ceria has a lower C-H activation energy which suggests that it is highly active and would offer better methane conversion. However, it also binds °¤CH3 strongly leading to over-oxidation of methane and thus gives low C2 selectivity. Conversely, high C-H activation energy and weak °¤CH3 adsorption imply that pure/doped MgO catalysts will have better C2 selectivity but low activity. Therefore, a trade-off between activity and selectivity is inherent in the active site. Sub-correlations to that shown in Figure 1 demonstrate that this correlation holds across a single material with increasing state of reduction as well as with change in U parameter used in the DFT+U method. Methods on finding an optimal trade-off in activity and selectivity, as well as potential approaches to breaking this correlation, will be discussed.
Figure 1. Correlation between surface reducibility and activity/selectivity
References
1. G. E. Keller, M. M. Bhasin, Journal of Catalysis 73 (1982) 9.
2. T. Ito, J.H. Lunsford, Nature 314 (1985) 721.
See more of this Group/Topical: Computational Molecular Science and Engineering Forum