Polymorphism and orientation control of copper-dicarboxylate metal–organic framework thin films through vapour- and liquid-phase growth

Víctor Rubio-Giménez; Francesco Carraro; Sebastian Hofer; Mario Fratschko; Timothée Stassin; Sabina Rodríguez-Hermida; Benedikt Schrode; Luisa Barba; Roland Resel; Paolo Falcaro; Rob Ameloot

doi:10.1039/D3CE01296D

Polymorphism and orientation control of copper-dicarboxylate metal–organic framework thin films through vapour- and liquid-phase growth†

Víctor Rubio-Giménez,

‡*^a Francesco Carraro,

‡^b Sebastian Hofer,^c Mario Fratschko,^c Timothée Stassin,

§^a Sabina Rodríguez-Hermida,¶^a Benedikt Schrode,

^c Luisa Barba,

^d Roland Resel,

*^c Paolo Falcaro

*^b and Rob Ameloot

*^a

Author affiliations

* Corresponding authors

^a Centre for Membrane Separations, Adsorption, Catalysis and Spectroscopy (cMACS), KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
E-mail: victorrubio.gimenez@kuleuven.be, rob.ameloot@kuleuven.be

^b Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9/Z2, 8010 Graz, Austria
E-mail: paolo.falcaro@tugraz.at

^c Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, 8010 Graz, Austria
E-mail: roland.resel@tugraz.at

^d Istituto di Cristallografia – Sincrotrone Elettra, Consiglio Nazionale delle Ricerche, Area Science Park, 34142 Basovizza, Italy

Abstract

Precise control over the crystalline phase and crystallographic orientation within thin films of metal–organic frameworks (MOFs) is highly desirable. Here, we report a comparison of the liquid- and vapour-phase film deposition of two copper-dicarboxylate MOFs starting from an oriented metal hydroxide precursor. X-ray diffraction revealed that the vapour- or liquid-phase reaction of the linker with this precursor results in different crystalline phases, morphologies, and orientations. Pole figure analysis showed that solution-based growth of the MOFs follows the axial texture of the metal hydroxide precursor, resulting in heteroepitaxy. In contrast, the vapour-phase method results in non-epitaxial growth with uniplanar texture only.

CrystEngComm

Polymorphism and orientation control of copper-dicarboxylate metal–organic framework thin films through vapour- and liquid-phase growth†

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Polymorphism and orientation control of copper-dicarboxylate metal–organic framework thin films through vapour- and liquid-phase growth

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