A Titanium(IV)-Based Metal-Organic Framework Featuring Defect-Rich Ti-O Sheets as an Oxidative Desulfurization Catalyst

Simon Smolders; Tom Willhammar; Andraž Krajnc; Kadir Sentosun; Michael T Wharmby; Kirill A Lomachenko; Sara Bals; Gregor Mali; Maarten B J Roeffaers; Dirk E De Vos; Bart Bueken

doi:10.1002/anie.201904347

A Titanium(IV)-Based Metal-Organic Framework Featuring Defect-Rich Ti-O Sheets as an Oxidative Desulfurization Catalyst

Angew Chem Int Ed Engl. 2019 Jul 1;58(27):9160-9165. doi: 10.1002/anie.201904347. Epub 2019 May 27.

Authors

Affiliations

¹ Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F p.o. box 2461, 3001, Leuven, Belgium.
² Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16C, 10691, Stockholm, Sweden.
³ Department of Inorganic Chemistry and Technology, National Institute of Chemistry, Hajdrihova 19, 1001, Ljubljana, Slovenia.
⁴ EMAT, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium.
⁵ Deutsches Elektronen-Synchrotron, Notkestraße 85, 22607, Hamburg, Germany.
⁶ European Synchrotron Radiation Facility, Avenue des Martyrs 71, CS 40220, 38043, Grenoble Cedex 9, France.

PMID: 31059170
DOI: 10.1002/anie.201904347

Abstract

While titanium-based metal-organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few Ti^IV MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK-47 is now presented, the first Ti carboxylate MOF based on sheets of Ti^IV O₆ octahedra, which can be synthesized with a range of different linkers. COK-47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes. Its structure was determined by continuous rotation electron diffraction and studied in depth by X-ray total scattering, EXAFS, and solid-state NMR. Furthermore, its photoactivity was investigated by electron paramagnetic resonance and demonstrated by catalytic photodegradation of rhodamine 6G.

Keywords: Ti-oxo sheets; metal-organic frameworks; oxidative desulfurization; photocatalysis; titanium.

Abstract

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