A quantitative multiscale perspective on primary olefin formation from methanol
Artikel i vetenskaplig tidskrift, 2021

The formation of the first C–C bond and primary olefins from methanol over zeolite and zeotype catalysts has been studied for over 40 years. Over 20 mechanisms have been proposed for the formation of the first C–C bond. In this quantitative multiscale perspective, we decouple the adsorption, desorption, mobility, and surface reactions of early species through a combination of vacuum and sub-vacuum studies using temporal analysis of products (TAP) reactor systems, and through studies with atmospheric fixed bed reactors. These results are supplemented with density functional theory calculations and data-driven physical models, using partial differential equations, that describe the temporal and spatial evolution of species. We consider the effects of steam, early degradation species, and product masking due to the inherent autocatalytic nature of the process, which all complicate the observation of the primary olefin(s). Although quantitative spectroscopic determination of the lifetimes, surface mobility, and reactivity of adspecies is still lacking in the literature, we observe that reaction barriers are competitive with adsorption enthalpies and/or activation energies of desorption, while facile diffusion occurs in the porous structures of the zeolite/zeotype catalysts. Understanding the various processes allows for quantitative evaluation of their competing energetics, which leads to molecular insights as to what governs the catalytic activity during the conversion of methanol to primary olefins over zeolite/zeotype catalysts.

Författare

Oluwatoyin Omojola

Chalmers, Mekanik och maritima vetenskaper, Strömningslära

Andrew Logsdail

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Park Place

Andre van Veen

The University of Warwick

Stefan Nasatase

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Park Place

Physical Chemistry Chemical Physics

1463-9076 (ISSN) 1463-9084 (eISSN)

Vol. 23 21437-21469

Ämneskategorier

Fysikalisk kemi

Kemiteknik

Teoretisk kemi

DOI

10.1039/D1CP02551A

Mer information

Skapat

2022-01-26