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Investigation of the preparation and reactivity of metal-organic frameworks of cerium and pyridine-2,4,6-tricarboxylate
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Fonseca de Lima, Juliana, Moreno, Fernanda V. S., Menezes, Bruno A. T., da Silva Barbosa, Jader, Waddington, Matthew C., Franklin, Siân A., Clarkson, Guy J., Walker, Marc, Serra, Osvaldo A. and Walton, Richard I. (2021) Investigation of the preparation and reactivity of metal-organic frameworks of cerium and pyridine-2,4,6-tricarboxylate. Dalton Transactions, 51 . pp. 145-155. doi:10.1039/d1dt03514b ISSN 1477-9226.
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Official URL: https://doi.org/10.1039/D1DT03514B
Abstract
The synthesis of three coordination polymers of cerium(III) and the ligand pyridine-2,4,6-tricarboxylate (PTC) is reported. Two of the materials crystallise under hydrothermal conditions at 180 °C, with [Ce(PTC)(H O) ]·1.5H O, (1), being formed on extended periods of reaction time, 3 days or longer, and Ce(PTC)(H O) , (2), crystallising after 1 day. Both phases contain Ce(III) but are prepared using the Ce(IV) salt Ce(SO ) ·4H O as reagent. Under solvothermal conditions (mixed water- , -dimethylformamide (DMF)), the phase [Ce(PTC)(H O)(DMF)]·H O (3) is crystallised. The structures of the three materials are resolved by single crystal X-ray diffraction, with the phase purity of the samples determined by powder X-ray diffraction and thermogravimetric analysis. (1) is constructed from helical chains cross-linked by the PTC linkers to give a three-dimensional structure that contains clusters of water molecules in channels that are hydrogen-bonded to each other and to additional waters that are coordinated to cerium. (2) also contains nine-coordinate cerium but these are linked to give a dense framework, in which water is directly coordinated to cerium. (3) contains corner-shared nine-coordinate cerium centres, linked to give a framework in which Ce-coordinated DMF fills space. Upon heating the material (1) in air all water is irreversibly lost to give a poorly crystalline anhydrous phase Ce(PTC), as deduced from X-ray thermodiffractometry and thermogravimetric analysis. The material (1), however, is hydrothermally stable, and is also stable under oxidising conditions, where immersion in 30% H O gives no loss in crystallinity. Oxidation of around 50% of surface Ce to the +4 oxidation state is thus possible, as evidenced by X-ray photoelectron spectroscopy, which is accompanied by a colour change from yellow to orange. Photocatalytic activity of (1) is screened and the material shows effective degradation of methyl orange.
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
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SWORD Depositor: | Library Publications Router | ||||||||
Library of Congress Subject Headings (LCSH): | Coordination polymers, Coordination polymers -- Synthesis, X-ray crystallography , X-rays -- Diffraction, Metal-organic frameworks , Cerium | ||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||
Publisher: | Royal Society of Chemistry | ||||||||
ISSN: | 1477-9226 | ||||||||
Official Date: | 6 December 2021 | ||||||||
Dates: |
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Volume: | 51 | ||||||||
Page Range: | pp. 145-155 | ||||||||
DOI: | 10.1039/d1dt03514b | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||
Date of first compliant deposit: | 22 December 2021 | ||||||||
Date of first compliant Open Access: | 23 December 2021 | ||||||||
RIOXX Funder/Project Grant: |
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