A quantitative multiscale perspective on primary olefin formation from methanol

Toyin Omojola, Andrew J. Logsdail, André C. Van Veen, Stefan Adrian F. Nastase

Research output: Contribution to journalArticlepeer-review

11 Citations (SciVal)

Abstract

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. This journal is

Original languageEnglish
Pages (from-to)21437-21469
Number of pages33
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number38
Early online date18 Aug 2021
DOIs
Publication statusPublished - 14 Oct 2021

Bibliographical note

Funding Information:
Toyin Omojola acknowledges financial support from the Petroleum Technology Development Fund (PTDF/ED/PHD/OO/766/15) for his PhD work conducted at the University of Bath and the University of Warwick and is grateful to the Royal Society of Chemistry, Society of Chemical Industry, Armourers and Brasiers Gauntlet Trust, University of Warwick, and the Alumni Travel Fund of the University of Bath for additional financial support. Stefan Adrian F. Nastase wishes to thank the School of Chemistry, Cardiff University for a PhD studentship. Andrew J. Logsdail acknowledges funding by the UKRI Future Leaders Fellowship program (MR/T018372/1). We are grateful to Dr Dmitry Lukyanov and Professor Richard Catlow for fruitful scientific discussions.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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