Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties.

The study presents an ab-initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF-vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first-principles-based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange-correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT-constrained microkinetic model optimization for other heterogeneously catalyzed systems.

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy.

Enthalpies of formation of adsorbates are crucial parameters in the microkinetic modeling of heterogeneously catalyzed reactions since they quantify the stability of intermediates on the catalyst surface. This quantity is often computed using density functional theory (DFT), as more accurate methods are computationally still too expensive, which means that the derived enthalpies have a large uncertainty. In this study, we propose a new error cancellation method to compute the enthalpies of formation of adsorbates from DFT more accurately through a generalized connectivity-based hierarchy. The enthalpy of formation is determined through a hypothetical reaction that preserves atomistic and bonding environments. The method is applied to a data set of 60 adsorbates on Pt(111) with up to 4 heavy (non-hydrogen) atoms. Enthalpies of formation of the fragments required for the bond balancing reactions are based on experimental heats of adsorption for Pt(111). The comparison of enthalpies of formation derived from different DFT functionals using the isodesmic reactions shows that the effect of the functional is significantly reduced due to the error cancellation. Thus, the proposed methodology creates an interconnected thermochemical network of adsorbates that combines experimental with ab initio thermochemistry in a single and more accurate thermophysical database.

Quantifying the Impact of Parametric Uncertainty on Automatic Mechanism Generation for CO2 Hydrogenation on Ni(111).

Automatic mechanism generation is used to determine mechanisms for the CO2 hydrogenation on Ni(111) in a two-stage process while considering the correlated uncertainty in DFT-based energetic parameters systematically. In a coarse stage, all the possible chemistry is explored with gas-phase products down to the ppb level, while a refined stage discovers the core methanation submechanism. Five thousand unique mechanisms were generated, which contain minor perturbations in all parameters. Global uncertainty assessment, global sensitivity analysis, and degree of rate control analysis are performed to study the effect of this parametric uncertainty on the microkinetic model predictions. Comparison of the model predictions with experimental data on a Ni/SiO2 catalyst find a feasible set of microkinetic mechanisms within the correlated uncertainty space that are in quantitative agreement with the measured data, without relying on explicit parameter optimization. Global uncertainty and sensitivity analyses provide tools to determine the pathways and key factors that control the methanation activity within the parameter space. Together, these methods reveal that the degree of rate control approach can be misleading if parametric uncertainty is not considered. The procedure of considering uncertainties in the automated mechanism generation is not unique to CO2 methanation and can be easily extended to other challenging heterogeneously catalyzed reactions.