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Complexity structures of active sites in catalysis

corresponding

MARCO PIUMETTI1*, NIKOS LYGEROS2
*Corresponding author
1. Department of Applied Science and Technology, Institute of Chemistry, Corso Duca degli Abruzzi 24, Politecnico di Torino, I-10129, Turin (Italy).
2.. LGPC (UMR 5285), Université de Lyon, 69616, Villeurbanne (France).

Abstract

Four types of solid catalysts, having different complexity structures, are considered in this mini-review to show the key role of self-organizing phenomena in catalysis: i) single-site heterogeneous catalysts; ii) supported metal nanoparticles; iii) zeolites and iv) transition metal oxides operating via redox cycles. These self-organizing phenomena are an intrinsic property of any catalyst and reflect different complexity structures, as the self-repair and reorganization of active sites, the mutual interactions between neighbouring sites, the mass transfer limitations (i.e. shape selective control), the dynamic networks of “sites-joined”, etc. Consequently, the catalytic process typically results in a non-linear combination of various complexity structures and hence catalytic behaviours may appear. All these aspects are considered in the present paper to illustrate the nature of active sites and their complexity in catalysis.


INTRODUCTION

Many investigations have confirmed that active sites are dynamic entities that can continuously change their physico-chemical properties depending on the reaction conditions (1,2).
It has been demonstrated that active centres may include more than one single site to form “reactive groups” (3). For instance, in the case of dissociative hydrogen adsorption on Pd(111) surface, an aggregate of three or more vacant sites is needed to form an active centre for efficient H2 dissociation, as revealed by dynamic STM analysis and DFT calculations (4, 5). Similarly, spectroscopic studies have shown that the activity of sulfonic acid resins for reactions taking place in a network of –SO3H groups (i.e. dehydration reactions of alcohols) is typical