A General and Robust Approach for Defining and Solving Microkinetic Catalytic Systems

作者：Gusmao Gabriel S; Christopher Phillip^*

来源：AIChE Journal, 2015, 61(1): 188-199.

DOI：10.1002/aic.14627

• microkinetics
• catalytic modeling
• analytical
• heterogeneous catalysts
• density functional theory calculations

Recent approaches for the rational design of heterogeneous catalysts have relied on first-principles-based microkinetic modeling to efficiently screen large phase spaces of catalytic materials for optimal activity and selectivity. Microkinetic modeling allows the calculation of catalytic rate and selectivity under a given set of conditions without a priori assumptions of rate or selectivity controlling steps by simultaneously solving nonlinear algebraic equations comprising species mass balances bound by the pseudo steady-state approximation. We introduce a general approach to define and solve microkinetic systems that relies solely on its stoichiometric matrix and kinetic parameters of considered reaction steps. Our approach relies on linearization of the microkinetic system, enabling analytical calculation of system derivatives for use in quasi-Newton solution schemes that exhibit excellent robustness and efficiency with minimal dependence on initial conditions.

• 出版日期2015-1