Tuning of gallery heights in a crystalline 2D carbon nitride network

Chong, Samantha Y., Jones, James T. A., Khimyak, Yaroslav Z., Cooper, Andrew I., Thomas, Arne, Antonietti, Markus and Bojdys, Michael J. (2013) Tuning of gallery heights in a crystalline 2D carbon nitride network. Journal of Materials Chemistry A, 1 (4). pp. 1102-1107. ISSN 2050-7488

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Abstract

Poly(triazine imide) - a 2D layered network - can be obtained as an intercalation compound with halides from the ionothermal condensation of dicyandiamide in a eutectic salt melt. The gallery height of the intercalated material can be tuned via the composition of the eutectic melt and by post-synthetic modification. Here, we report the synthesis of poly(triazine imide) with intercalated bromide ions (PTI/Br) from a lithium bromide and potassium bromide salt melt. PTI/Br has a hexagonal unit-cell (P63cm (no. 185); a = 8.500390(68) Å, c = 7.04483(17) Å) that contains two layers of imide-bridged triazine (C3N3) units stacked in an AB-fashion as corroborated by solid-state NMR, FTIR spectroscopy and high-resolution TEM. By comparison with a recently reported material PTI/Li +Cl-, prepared from a LiCl/KCl eutectic, the layer-stacking distance in the analogous bromide material was expanded from 3.38 Å to 3.52 Å-an exceptionally large spacing for an aromatic, discotic system (cf. graphite 3.35 Å). Subsequent treatment of PTI/Br with concentrated ammonium fluoride yields poly(triazine imide) with intercalated fluoride ions (PTI/F) (P63/m (no. 176); a = 8.4212(4) Å, c = 6.6381(5) Å) as a statistical phase mix with PTI/Br. Fluoride intercalation leads to a contraction of the gallery height to 3.32 Å, demonstrating that the gallery height is synthetically tuneable in these materials.

Item Type: Article
Uncontrolled Keywords: chemistry(all),renewable energy, sustainability and the environment,materials science(all),sdg 7 - affordable and clean energy ,/dk/atira/pure/subjectarea/asjc/1600
Faculty \ School: Faculty of Science > School of Pharmacy (former - to 2024)
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Depositing User: LivePure Connector
Date Deposited: 09 Jul 2021 07:28
Last Modified: 06 Feb 2025 09:57
URI: https://ueaeprints.uea.ac.uk/id/eprint/80479
DOI: 10.1039/c2ta01068b

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