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Aluminium speciation in 1-Butyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures Rocher, Nathalie M., Izgorodina, Ekaterina I., Rüther, Thomas, Forsyth, Maria, MacFarlane, Douglas R., Rodopoulos, Theo, Horne, Michael D. and Bond, Alan M. 2008, Aluminium speciation in 1-Butyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures, Chemistry - a European journal, vol. 15, no. 14, pp. 3435-3447. Attached Files Name Description MIMEType Size Downloads Title Aluminium speciation in 1-Butyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures Author(s) Rocher, Nathalie M. Izgorodina, Ekaterina I. Rüther, Thomas Forsyth, Maria MacFarlane, Douglas R. Rodopoulos, Theo Horne, Michael D. Bond, Alan M. Journal name Chemistry - a European journal Volume number 15 Issue number 14 Start page 3435 End page 3447 Total pages 13 Publisher Wiley - V C H Verlag GmbH & Co. KGaA Place of publication Weinheim, Germany Publication date 2008-03-23 ISSN 0947-6539 1521-3765 Keyword(s) ab initio calculations aluminum electrodeposition ionic liquids NMR spectroscopy Raman spectroscopy Summary Aluminium speciation: Aluminium speciation in NTf2 ionic liquids has a strong influence on its electrodeposition from the liquid mixture. This work probed the nature of these species and proposes that the electroactive species involved are either [AlCl3(NTf2)]− or [AlCl2(NTf2)2]− (e.g., see figure). Electrodeposition of aluminium is possible from solutions of AlCl3 dissolved in the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (C4mpyrNTf2) ionic liquid. However, electrodeposition is dependant on the AlCl3 concentration as it only occurs at concentrations >1.6 mol L−1. At these relatively high AlCl3 concentrations the C4mpyrNTf2/AlCl3 mixtures exhibit biphasic behaviour. Notably, at 1.6 mol L−1 AlCl3, aluminium can only be electrodeposited from the upper phase. Conversely, we found that at 3.3 mol L−1 aluminium electrodeposition can only occur from the lower phase. The complex chemistry of the C4mpyrNTf2/AlCl3 system is described and implications of aluminium speciation in several C4mpyrNTf2/AlCl3 mixtures, as deduced from Raman and 27Al NMR spectroscopic data, are discussed. The 27Al NMR spectra of the C4mpyrNTf2/AlCl3 mixtures revealed the presence of both tetrahedrally and octahedrally coordinated aluminium species. Raman spectroscopy revealed that the level of uncoordinated NTf2− anions decreased with increasing AlCl3 concentration. Quantum chemical calculations using density functional and ab initio theory were employed to identify plausible aluminium-containing species and to calculate their vibrational frequencies, which in turn assisted the assignment of the observed Raman bands. The data indicate that the electroactive species involved are likely to be either [AlCl3(NTf2)]− or [AlCl2(NTf2)2]−. Language eng Field of Research 039999 Chemical Sciences not elsewhere classified Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences HERDC Research category C1.1 Refereed article in a scholarly journal Copyright notice ©2009, Wiley-VCH Verlag GmbH&Co. KGaA Persistent URL http://hdl.handle.net/10536/DRO/DU:30030244 Document type: Journal Article Collection: Institute for Technology Research and Innovation Related Links Link Description Connect to published version (restricted access) Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Versions Version Filter Type Fri, 10 Sep 2010, 15:10:59 EST Tue, 12 Oct 2010, 14:57:52 EST Tue, 12 Oct 2010, 14:59:51 EST Tue, 12 Oct 2010, 15:00:42 EST Mon, 27 Feb 2012, 15:35:28 EST Mon, 16 Jun 2014, 16:28:20 EST Thu, 11 Dec 2014, 16:44:39 EST Filtered Full Citation counts:   Cited 24 times in TR Web of Science Cited 25 times in Scopus Search Google Scholar Access Statistics: 384 Abstract Views, 1 File Downloads  -  Detailed Statistics Created: Fri, 10 Sep 2010, 15:10:59 EST

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