Aluminium speciation in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures

Chemistry : a European Journal
Nathalie M RocherAlan M Bond

Abstract

Electrodeposition of aluminium is possible from solutions of AlCl(3) dissolved in the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (C(4)mpyrNTf(2)) ionic liquid. However, electrodeposition is dependant on the AlCl(3) concentration as it only occurs at concentrations >1.6 mol L(-1). At these relatively high AlCl(3) concentrations the C(4)mpyrNTf(2)/AlCl(3) mixtures exhibit biphasic behaviour. Notably, at 1.6 mol L(-1) AlCl(3), 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 C(4)mpyrNTf(2)/AlCl(3) system is described and implications of aluminium speciation in several C(4)mpyrNTf(2)/AlCl(3) mixtures, as deduced from Raman and (27)Al NMR spectroscopic data, are discussed. The (27)Al NMR spectra of the C(4)mpyrNTf(2)/AlCl(3) mixtures revealed the presence of both tetrahedrally and octahedrally coordinated aluminium species. Raman spectroscopy revealed that the level of uncoordinated NTf(2)(-) anions decreased with increasing AlCl(3) concentration. Quantum chemical calculations using density functional and ab initio theory were employed to identify plausible aluminiu...Continue Reading

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Citations

Jan 5, 2017·Chemical Reviews·Vitor H PaschoalMauro C C Ribeiro
Jul 1, 2016·Advanced Materials·Giuseppe Antonio EliaRobert Hahn
Dec 15, 2015·Physical Chemistry Chemical Physics : PCCP·Tristan J SimonsDouglas R MacFarlane
Jan 1, 2015·Chemical Science·Aaron ElbourneRob Atkin
Mar 19, 2011·Chemistry : a European Journal·Neil R BrooksJan Fransaer
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Feb 11, 2010·Physical Chemistry Chemical Physics : PCCP·Douglas R MacFarlaneMaria Forsyth
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