Propagating DFT Uncertainty to Mechanism Determination, Degree of Rate Control and Coverage Analysis: The Kinetics of Dry Reforming of Methane

Catalytic processes are rather complex in which a large number of reaction pathways are possible, and identifying the preferred reaction pathway either from experiments or theoretical modeling is rather challenging. The approach combining density functional theory (DFT) calculations and microkinetic modeling is receiving increasing attentions recently to gain more insight into surface catalytic reactions. However, the error propagation from DFT to those properties determined remains largely overlooked in the literature. In order to assess the uncertainty of the DFT-determined mechanisms and kinetics of the dry reforming of methane (DRM) reaction over Ni(111) and Pt(111), we employed the well-trained Bayesian error estimation functional with van der Waals correlation (BEEF-vdW) tailored for describing surface chemical properties in the DFT calculations. With a large ensemble of 2000 exchange-correlation functionals generated around the optimal BEEF-vdW functional, an ensemble of DFT energetics can be calcu...