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XAFS studies of Ni, Ta, and Nb chlorides in the ionic liquid 1-ethyl-3-methyl imidazolium chloride/aluminum chloride

Published online by Cambridge University Press:  05 March 2012

W. E. O’Grady ,
D. F. Roeper ,
K. I. Pandya  and
G. T. Cheek
W. E. O’Grady*
Affiliation:
Naval Research Laboratory, Code 6130, Washington, District of Columbia 20375
D. F. Roeper
Affiliation:
Naval Research Laboratory, Code 6130, Washington, District of Columbia 20375 andEXCET, Inc., Springfield, Virginia
K. I. Pandya
Affiliation:
SAIC, Brookhaven National Laboratory, Upton, New York 11973
G. T. Cheek
Affiliation:
Chemistry Department, US Naval Academy, Annapolis, Maryland 21402
*
a)Author to whom correspondence should be addressed. Electronic mail: ogrady@nrl.navy.mil
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Abstract

The structures of anhydrous nickel, niobium, and tantalum chlorides have been investigated in situ in acidic and basic ionic liquids (ILs) of 1-methyl-3-ethylimidazolium chloride (EMIC)/AlCl3 with X-ray absorption spectroscopy (XAS). The coordination of NiCl2 changes from tetrahedral in basic solution to octahedral in acidic solution. The NiCl2 is a strong Lewis acid in that it can induce the AlCl3 to share its chlorides in the highly acidic IL, forming a structure with six near Cl− ions and eight further distant Al ions which share the chloride ions surrounding the Ni2+. When Nb2Cl10, a dimer, is added to the acidic or basic solution, the dimer breaks apart and forms two species. In the acid solution, two trigonal bipyramids are formed with five equal chloride distances, while in the basic solution, a square pyramid with four chlorides forming a square base and one shorter axial chloride bond. Ta2Cl10 is also a dimer and divides into half in the acidic solution and forms two trigonal bipyramids. In the basic solution, the dimer breaks apart but the species formed is sufficiently acidic that it attracts two additional chloride ions and forms a seven coordinated tantalum species.

Keywords

X-ray absorption spectroscopyXASionic liquidnickel chlorideniobium chloridetantalum chloride
Type
Technical Articles
Information
Powder Diffraction , Volume 26 , Special Issue 2 , June 2011 , pp. 171 - 175
Copyright
Copyright © Cambridge University Press 2011

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