Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties**
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- School of Engineering Brown University 184 Hope Street Providence RI 02912 USA, Institute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 20 76128 Karlsruhe Germany
- Institute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 20 76128 Karlsruhe Germany
- Institute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 20 76128 Karlsruhe Germany, Institute of Catalysis Research and Technology Karlsruhe Institute of Technology 76344 Eggenstein-Leopoldshafen Germany
- School of Chemical and Biomolecular Engineering Atlanta GA 30318 USA
- School of Engineering Brown University 184 Hope Street Providence RI 02912 USA
Abstract 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.
- Research Organization:
- Brown University, Providence, RI (United States)
- Sponsoring Organization:
- USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0019441
- OSTI ID:
- 1996312
- Journal Information:
- Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 39 Vol. 62; ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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