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Overcoming Crystallinity Limitations of Aluminium Metal–Organic Frameworks by Oxalic Acid Modulated Synthesis

submitted on 17.10.2019, 21:00 and posted on 21.10.2019, 21:04 by Stefano Canossa, Adrian Gonzalez-Nelson, Leonid Shupletsov, María del Carmen Martín, Monique van der Veen
A modulated synthesis approach based on the chelating properties of oxalic acid (H2C2O4) is presented as a robust and versatile method to achieve highly crystalline Al-based metal–organic frameworks (MOFs). A comparative study on this method and the already established modulation by hydrofluoric acid was conducted using MIL-53 as test system. The superior performance of oxalic acid modulation in terms of crystallinity and absence of undesired impurities is explained by assessing the coordination modes of the two modulators and the structural features of the product. The validity of our approach was confirmed for a diverse set of Al-MOFs, namely X-MIL-53 (X = OH, CH3O, Br, NO2), CAU-10, MIL-69, and Al(OH)ndc (ndc = 1,4-naphtalenedicarboxylate), highlighting the potential benefits of extending the use of this modulator to other coordination materials.


This work was funded by the European Research Council (grant number 759212) within the Horizon 2020 Framework Programme (H2020-EU.1.1)

The work by A.G.-N. forms part of the research programme of DPI, NEWPOL project 731.015.506.


Email Address of Submitting Author


Delft University of Technology


The Netherlands

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest