Modeling and Simulation of Heterogeneous Catalytic Reactions -- Contents -- Preface -- List of Contributors -- 1 Modeling Catalytic Reactions on Surfaces with Density Functional Theory -- 1.1 Introduction -- 1.2 Theoretical Background -- 1.2.1 The Many-Body Problem -- 1.2.2 Born-Oppenheimer Approximation -- 1.2.3 Wave Function-Based Methods -- 1.2.3.1 Hartree-Fock Approximation -- 1.2.3.2 Post Hartree-Fock Methods -- 1.2.4 Density-Based Methods -- 1.2.4.1 The Thomas-Fermi Model -- 1.2.4.2 The Hohenberg-Kohn Theorems -- 1.2.4.3 The Kohn-Sham Equations -- 1.2.4.4 Exchange-Correlation Functionals -- 1.2.5 Technical Aspects of Modeling Catalytic Reactions -- 1.2.5.1 Geometry Optimizations -- 1.2.5.2 Transition-State Optimizations -- 1.2.5.3 Vibrational Frequencies -- 1.2.5.4 Thermodynamic Treatments of Molecules -- 1.2.5.5 Considering Solvation -- 1.2.6 Model Representation -- 1.2.6.1 Slab/Supercell Approach -- 1.2.6.2 Cluster Approach -- 1.3 The Electrocatalytic Oxygen Reduction Reaction on Pt(111) -- 1.3.1 Water Formation from Gaseous O2 and H2 -- 1.3.1.1 O2 Dissociation -- 1.3.1.2 OOH Formation -- 1.3.1.3 HOOH Formation -- 1.3.2 Simulations Including Water Solvation -- 1.3.2.1 Langmuir-Hinshelwood Mechanisms -- 1.3.2.2 Eley-Rideal Reactions -- 1.3.3 Including Thermodynamical Quantities -- 1.3.3.1 Langmuir-Hinshelwood and Eley-Rideal Mechanisms -- 1.3.4 Including an Electrode Potential -- 1.4 Conclusions -- References -- 2 Dynamics of Reactions at Surfaces -- 2.1 Introduction -- 2.2 Theoretical and Computational Foundations of Dynamical Simulations -- 2.3 Interpolation of Potential Energy Surfaces -- 2.4 Quantum Dynamics of Reactions at Surfaces -- 2.5 Nondissociative Molecular Adsorption Dynamics -- 2.6 Adsorption Dynamics on Precovered Surfaces -- 2.7 Relaxation Dynamics of Dissociated H2 Molecules.

2.8 Electronically Nonadiabatic Reaction Dynamics -- 2.9 Conclusions -- References -- 3 First-Principles Kinetic Monte Carlo Simulations for Heterogeneous Catalysis: Concepts, Status, and Frontiers -- 3.1 Introduction -- 3.2 Concepts and Methodology -- 3.2.1 The Problem of a Rare Event Dynamics -- 3.2.2 State-to-State Dynamics and kMC Trajectories -- 3.2.3 kMC Algorithms: from Basics to Efficiency -- 3.2.4 Transition State Theory -- 3.2.5 First-Principles Rate Constants and the Lattice Approximation -- 3.3 A Showcase -- 3.3.1 Setting up the Model: Lattice, Energetics, and Rate Constant Catalog -- 3.3.2 Steady-State Surface Structure and Composition -- 3.3.3 Parameter-Free Turnover Frequencies -- 3.3.4 Temperature-Programmed Reaction Spectroscopy -- 3.4 Frontiers -- 3.5 Conclusions -- References -- 4 Modeling the Rate of Heterogeneous Reactions -- 4.1 Introduction -- 4.2 Modeling the Rates of Chemical Reactions in the Gas Phase -- 4.3 Computation of Surface Reaction Rates on a Molecular Basis -- 4.3.1 Kinetic Monte Carlo Simulations -- 4.3.2 Extension of MC Simulations to Nanoparticles -- 4.3.3 Reaction Rates Derived from MC Simulations -- 4.3.4 Particle-Support Interaction and Spillover -- 4.3.5 Potentials and Limitations of MC Simulations for Derivation of Overall Reaction Rates -- 4.4 Models Applicable for Numerical Simulation of Technical Catalytic Reactors -- 4.4.1 Mean Field Approximation and Reaction Kinetics -- 4.4.2 Thermodynamic Consistency -- 4.4.3 Practicable Method for Development of Multistep Surface Reaction Mechanisms -- 4.4.4 Potentials and Limitations of the Mean Field Approximation -- 4.5 Simplifying Complex Kinetic Schemes -- 4.6 Summary and Outlook -- References -- 5 Modeling Reactions in Porous Media -- 5.1 Introduction -- 5.2 Modeling Porous Structures and Surface Roughness -- 5.3 Diffusion -- 5.4 Diffusion and Reaction.

5.5 Pore Structure Optimization: Synthesis -- 5.6 Conclusion -- References -- 6 Modeling Porous Media Transport, Heterogeneous Thermal Chemistry, and Electrochemical Charge Transfer -- 6.1 Introduction -- 6.2 Qualitative Illustration -- 6.3 Gas-Phase Conservation Equations -- 6.3.1 Gas-Phase Transport -- 6.3.2 Chemical Reaction Rates -- 6.3.3 Boundary Conditions -- 6.4 Ion and Electron Transport -- 6.5 Charge Conservation -- 6.5.1 Effective Properties -- 6.5.2 Boundary Conditions -- 6.5.3 Current Density and Cell Potential -- 6.6 Thermal Energy -- 6.7 Chemical Kinetics -- 6.7.1 Thermal Heterogeneous Kinetics -- 6.7.2 Charge Transfer Kinetics -- 6.7.3 Butler-Volmer Formulation -- 6.7.4 Elementary and Butler-Volmer Formulations -- 6.8 Computational Algorithm -- 6.9 Button Cell Example -- 6.9.1 Polarization Characteristics -- 6.9.2 Electric Potentials and Charged Species Fluxes -- 6.9.3 Anode Gas-Phase Profiles -- 6.9.4 Anode Surface Species Profiles -- 6.9.5 Applicability and Extensibility -- 6.10 Summary and Conclusions -- 6.10.1 Greek Letters -- References -- 7 Evaluation of Models for Heterogeneous Catalysis -- 7.1 Introduction -- 7.2 Surface and Gas-Phase Diagnostic Methods -- 7.2.1 Surface Science Diagnostics -- 7.2.2 In Situ Gas-Phase Diagnostics -- 7.3 Evaluation of Hetero/Homogeneous Chemical Reaction Schemes -- 7.3.1 Fuel-Lean Combustion of Methane/Air on Platinum -- 7.3.1.1 Heterogeneous Kinetics -- 7.3.1.2 Gas-Phase Kinetics -- 7.3.2 Fuel-Lean Combustion of Propane/Air on Platinum -- 7.3.3 Fuel-Lean Combustion of Hydrogen/Air on Platinum -- 7.3.4 Fuel-Rich Combustion of Methane/Air on Rhodium -- 7.3.5 Application of Kinetic Schemes in Models for Technical Systems -- 7.4 Evaluation of Transport -- 7.4.1 Turbulent Transport in Catalytic Systems -- 7.4.2 Modeling Directions in Intraphase Transport -- 7.5 Conclusions -- References.

8 Computational Fluid Dynamics of Catalytic Reactors -- 8.1 Introduction -- 8.2 Modeling of Reactive Flows -- 8.2.1 Governing Equations of Multicomponent Flows -- 8.2.2 Turbulent Flows -- 8.2.3 Three-Phase Flow -- 8.2.4 Momentum and Energy Equations for Porous Media -- 8.3 Coupling of the Flow Field with Heterogeneous Chemical Reactions -- 8.3.1 Given Spatial Resolution of Catalyst Structure -- 8.3.2 Simple Approach for Modeling the Catalyst Structure -- 8.3.3 Reaction Diffusion Equations -- 8.3.4 Dusty Gas Model -- 8.4 Numerical Methods and Computational Tools -- 8.4.1 Numerical Methods for the Solution of the Governing Equations -- 8.4.2 CFD Software -- 8.4.3 Solvers for Stiff ODE and DAE Systems -- 8.5 Reactor Simulations -- 8.5.1 Flow through Channels -- 8.5.2 Monolithic Reactors -- 8.5.3 Fixed Bed Reactors -- 8.5.4 Wire Gauzes -- 8.5.5 Catalytic Reactors with Multiphase Fluids -- 8.5.6 Material Synthesis -- 8.5.7 Electrocatalytic Devices -- 8.6 Summary and Outlook -- References -- 9 Perspective of Industry on Modeling Catalysis -- 9.1 The Industrial Challenge -- 9.2 The Dual Approach -- 9.3 The Role of Modeling -- 9.3.1 Reactor Models -- 9.3.2 Surface Science and Breakdown of the Simplified Approach -- 9.3.3 Theoretical Methods -- 9.4 Examples of Modeling and Scale-Up of Industrial Processes -- 9.4.1 Ammonia Synthesis -- 9.4.2 Syngas Manufacture -- 9.4.2.1 Steam Reforming -- 9.4.2.2 Autothermal Reforming -- 9.5 Conclusions -- References -- 10 Perspectives of the Automotive Industry on the Modeling of Exhaust Gas Aftertreatment Catalysts -- 10.1 Introduction -- 10.2 Emission Legislation -- 10.3 Exhaust Gas Aftertreatment Technologies -- 10.4 Modeling of Catalytic Monoliths -- 10.5 Modeling of Diesel Particulate Filters -- 10.6 Selective Catalytic Reduction by NH3 (Urea-SCR) Modeling -- 10.6.1 Kinetic Analysis and Chemical Reaction Modeling.

10.6.1.1 NH3 Adsorption, Desorption, and Oxidation -- 10.6.1.2 NO-SCR Reaction -- 10.6.1.3 NH3-NO-NO2 Reactions -- 10.6.2 Influence of Washcoat Diffusion -- 10.7 Diesel Oxidation Catalyst, Three-Way Catalyst, and NOx Storage and Reduction Catalyst Modeling -- 10.7.1 Diesel Oxidation Catalyst -- 10.7.2 Three-Way Catalyst -- 10.7.3 NOx Storage and Reduction Catalyst -- 10.7.3.1 Species Transport Effects Related to NSCR: Shrinking Core Model -- 10.7.3.2 NH3 Formation During Rich Operation within a NSRC -- 10.8 Modeling Catalytic Effects in Diesel Particulate Filters -- 10.9 Determination of Global Kinetic Parameters -- 10.10 Challenges for Global Kinetic Models -- 10.11 System Modeling of Combined Exhaust Aftertreatment Systems -- 10.12 Conclusion -- References -- Index.