From the Molecular to the Reactor Scale with Accurate and Efficient Computational Frameworks for Reaction Kinetics

20 October 2016
Michail Stamatakis

Modelling catalytic kinetics is indispensable for the design of reactors and chemical processes. However, developing accurate and computationally efficient kinetic models remains challenging. Empirical kinetic models incorporate assumptions about rate-limiting steps and may thus not be applicable to operating regimes far from those where they were derived. Detailed microkinetic modelling approaches overcome this issue by accounting for all elementary steps of a reaction mechanism. However, the majority of such kinetic models employ mean-field approximations and are formulated as ordinary differential equations, which neglect spatial correlations. On the other hand, kinetic Monte Carlo (KMC) approaches provide a discrete-space continuous-time stochastic formulation that enables a detailed treatment of spatial correlations in the adlayer (resulting for instance from adsorbate-adsorbate lateral interactions), but at a significant computation expense.1,2

Motivated by these challenges, we discuss the necessity of KMC descriptions that incorporate detailed models of lateral interactions. Focusing on a titration experiment involving the oxidation of pre-adsorbed O by CO gas on Pd(111), we discuss experimental findings that show first order kinetics at low temperature (190 K) and half order kinetics at high temperature (320 K), the latter previously attributed to island formation.3 We perform KMC simulations whereby coverage effects on reaction barriers are captured by cluster expansion Hamiltonians and Brønsted-Evans-Polanyi (BEP) relations.4 By quantifying the effect of adlayer structure versus coverage effects on the observed kinetics, we rationalise the experimentally observed kinetics. We show that coverage effects lead to the half order kinetics at 320 K, rather than O-island formation as previously thought.5,6

Subsequently, we discuss our ongoing work in the development of approximations that capture such coverage effects but are much more computationally efficient than KMC, making it possible to use such models in reactor design. We focus on a model for NO oxidation incorporating first nearest neighbour lateral interactions and construct a sequence of approximations of progressively higher accuracy, starting from the mean-field treatment and continuing with a sequence of Bethe-Peierls models with increasing cluster sizes. By comparing the turnover frequencies of these models with those obtained from KMC simulation, we show that the mean-field predictions deviate by several orders of magnitude from the KMC results, whereas the Bethe-Peierls models exhibit progressively higher accuracy as the size of the explicitly treated cluster increases. While more computationally intensive than mean-field, these models still enable significant computational savings compared to a KMC simulation, thereby paving the road for employing them in multiscale modelling frameworks.


1    M. Stamatakis and D. G. Vlachos, ACS Catal. 2 (12), 2648 (2012).

2    M. Stamatakis, J Phys-Condens Mat 27 (1), 013001 (2015).

3    I. Nakai, H. Kondoh, T. Shimada, A. Resta, J. N. Andersen, and T. Ohta, J. Chem. Phys. 124 (22), 224712 (2006).

4    J. Nielsen, M. d’Avezac, J. Hetherington, and M. Stamatakis, J. Chem. Phys. 139 (22), 224706 (2013).

5    M. Stamatakis and S. Piccinin, ACS Catal. 6 (3), 2105 (2016).

6    S. Piccinin and M. Stamatakis, ACS Catal. 4, 2143 (2014).

  • Industrial and Applied Mathematics Seminar