Violations of Löwenstein's rule in zeolites

Fletcher, Rachel E.; Ling, Sanliang; Slater, Ben

Abstract

Zeolites, microporous aluminosilicates, are amongst the most widely used catalysts in the petrochemical industry. Zeolite catalytic functionality is influenced by the location of tetrahedral alumina and associated counter-cations in the aluminosilicate framework, yet little is definitively known about the factors that govern the framework aluminium arrangement. It is generally accepted that all zeolites obey Löwenstein's rule of “aluminium avoidance”, and that –Al–O–Al– bond formation is forbidden. Here, we describe an unprecedented screening of aluminium distribution in catalytically active zeolite SSZ-13 (CHA) in both its protonated and sodium-containing forms, H-SSZ-13 and Na-SSZ-13, using density functional theory (DFT). We predict violations of Löwenstein's rule in high and low silica H-SSZ-13 and other protonated frameworks considered in this investigation: H-LTA, H-RHO, H-ABW and H-MOR. The synthetic realisation of these zeolites could spur the development of new catalytic routes and materials, and the optimisation of existing zeolite catalysts.

Citation

Fletcher, R. E., Ling, S., & Slater, B. (2017). Violations of Löwenstein's rule in zeolites. Chemical Science, 8(11), 7483-7491. https://doi.org/10.1039/c7sc02531a

• Journal Article Type: Article
• Acceptance Date: Sep 5, 2017
• Online Publication Date: Sep 5, 2017
• Publication Date: Sep 5, 2017
• Deposit Date: Nov 20, 2018
• Journal: Chem. Sci.
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 8
• Issue: 11
• Pages: 7483-7491
• DOI: https://doi.org/10.1039/c7sc02531a
• Public URL: https://nottingham-repository.worktribe.com/output/1287492
• Publisher URL: https://pubs.rsc.org/en/Content/ArticleLanding/2017/SC/C7SC02531A#!divAbstract
• Additional Information: : This document is Similarity Check deposited; : Supplementary Information; : Rachel E. Fletcher (ORCID); : Rachel E. Fletcher (ResearcherID); : Sanliang Ling (ORCID); : Ben Slater (ORCID); : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0); : Single-blind; : Received 6 June 2017; Accepted 5 September 2017; Accepted Manuscript published 5 September 2017; Advance Article published 20 September 2017; Version of Record published 23 October 2017