Scaling Relations for Acidity and Reactivity of Zeolites.

Zeolites are widely applied as solid acid catalysts in various technological processes. In this work we have computationally investigated how catalytic reactivity scales with acidity for a range of zeolites with different topologies and chemical compositions. We found that straightforward correlations are limited to zeolites with the same topology. The adsorption energies of bases such as carbon monoxide (CO), acetonitrile (CH3 CN), ammonia (NH3 ), trimethylamine (N(CH3 )3 ), and pyridine (C5 H5 N) give the same trend of acid strength for FAU zeolites with varying composition. Crystal orbital Hamilton populations (COHP) analysis provides a detailed molecular orbital picture of adsorbed base molecules on the Brønsted acid sites (BAS). Bonding is dominated by strong σ donation from guest molecules to the BAS for the adsorbed CO and CH3 CN complexes. An electronic descriptor of acid strength is constructed based on the bond order calculations, which is an intrinsic parameter rather than adsorption energy that contains additional contributions due to secondary effects such as van der Waals interactions with the zeolite walls. The bond order parameter derived for the CH3 CN adsorption complex represents a useful descriptor for the intrinsic acid strength of FAU zeolites. For FAU zeolites the activation energy for the conversion of π-adsorbed isobutene into alkoxy species correlates well with the acid strength determined by the NH3 adsorption energies. Other zeolites such as MFI and CHA do not follow the scaling relations obtained for FAU; we ascribe this to the different van der Waals interactions and steric effects induced by zeolite framework topology.