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Etching and Polymerization Reactions of Alkoxythiophenes in HKUST-1: Choosing Between Filled and Core-Shell MOF/Polymer Composite Structures

preprint
revised on 25.02.2021, 18:26 and posted on 26.02.2021, 08:47 by William James, Colette M. Sullivan, Nicholas Marshall
In an earlier report, we found that neat 3,4-ethylenedioxythiophene (EDOT) directly reacts with HKUST-1 to form a core-shell composite in which the HKUST-1 surface is coated with conjugated polymer, while unsubstituted thiophenes formed a filled composite where polythiophene is contained in the MOF's pores. In this work, we found that EDOT and 3-methoxythiophene (3MOT), which react in the neat form to form core-shell composites, can be loaded into HKUST-1 pores without reaction when dissolved in hexanes. To a lesser extent, 3-hexyloxythiophene (3HOT) can be loaded in the same way. These hexane-loaded composites can then be heated, resulting in the formation of a 'filled' composite. This finding allows us to choose to prepare either a core-shell or a filled composite by selecting reaction conditions. The process of heating with alkoxythiophenes results in a morphology change in the HKUST-1 material. Composites were characterized by nitrogen sorption measurements, powder X-ray diffraction, and vibrational spectroscopy.

Funding

DOE WORC II

USC OVPR ASPIRE I

History

Email Address of Submitting Author

nicholasm@usca.edu

Institution

University of South Carolina Aiken

Country

United States

ORCID For Submitting Author

0000-0001-8048-0857

Declaration of Conflict of Interest

The authors declare no conflicts.

Version Notes

This is the version first submitted for peer-reviewed publication. Some data has been added to the SI and some assignments in the PXRD pattern have been corrected.

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