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Insights into the mechanochemical synthesis of MOF-74

DOI: 10.1021/acs.cgd.1c00213 DOI Help

Authors: Jethro Beamish-Cook (University of Reading) , Kenneth Shankland (University of Reading) , Claire A. Murray (Diamond Light Source) , Paz Vaqueiro (University of Reading)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Crystal Growth & Design

State: Published (Approved)
Published: April 2021
Diamond Proposal Number(s): 17320

Open Access Open Access

Abstract: Mechanochemical synthesis has recently emerged as a scalable “green” approach for the preparation of MOFs, but current understanding of the underlying reaction mechanisms is limited. In this work, an investigation of the reaction pathway of the mechanochemical synthesis of MOF-74 from ZnO and 2,5-dihydroxyterephthalic acid (H4HDTA), using DMF as a liquid additive, is presented. The complex reaction pathway involves the formation of four short-lived intermediate phases, prior to the crystallization of MOF-74. The crystal structures of three of these intermediates have been determined using a combination of single-crystal and powder X-ray diffraction methods and are described here. The initial stages of the reaction are very fast, with a DMF solvate of H4HDTA forming after only 2 min of milling. This is followed by crystallization, after only 4 min of milling, of a triclinic one-dimensional coordination polymer, Zn(H2DHTA)(DMF)2(H2O)2, which converts into a monoclinic polymorph on additional milling. Highly crystalline MOF-74 appears after prolonged milling, for at least 70 min.

Journal Keywords: Granular materials; Oxides; Crystal structure; Metal organic frameworks; Diffraction

Diamond Keywords: Gas Separation

Subject Areas: Chemistry, Materials

Instruments: I11-High Resolution Powder Diffraction

Added On: 02/05/2021 22:18


Discipline Tags:

Physical Chemistry Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction