Validation and Mechanistic Studies of the Headspace Effect in MOF Synthesis

Donovan, Julia C.; Wright, Keenan R.; Matzger, Adam J.

doi:10.1002/anie.202500531

Title: Validation and Mechanistic Studies of the Headspace Effect in MOF Synthesis

Journal Article · 14 February 2025 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202500531 · OSTI ID:2531279

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Department of Chemistry Institution University of Michigan Address 930 North University Avenue Ann Arbor Michigan 48109-1055 United States
Charles G. Overberger Collegiate Professor of Chemistry, and Macromolecular Science &, Engineering Department of Chemistry and Macromolecular Science and Engineering Program Institution University of Michigan Address 930 North University Avenue Ann Arbor Michigan 48109-1055 United States

Abstract The influence of headspace volume and composition on metal–organic framework (MOF) synthesis has been largely overlooked with no mechanisms currently invoking these factors. Herein, we reveal that an increased volume of oxygen in the headspace during the synthesis of zinc carboxylate‐based MOFs (MOF‐5, MOF‐177, and IRMOF‐8) as well as UiO‐66 and ZJU‐28 accelerates crystal formation. Investigation into the underlying mechanism of this phenomenon elucidates the critical roles played by all reagents, and some of their byproducts, in MOF synthesis. These insights are the key to developing more efficient and sustainable synthetic strategies for MOF production.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0004888

OSTI ID:: 2531279

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 12 Vol. 64; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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