期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 114, 期 39, 页码 12614-12622出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp106762b
关键词
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资金
- U.S. Department of Energy's (DOE)
- Biosciences and Geosciences
- NSERC
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- University of Washington
- Simon Fraser University
- Pacific Northwest National Laboratory
- Advanced Photon Source
We studied the coordination environment about Cu(II) in a pure ionic liquid, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), and in binary mixtures of this compound with water across the entire range of compositions, using a combination of X-ray absorption line structure (XAFS), ultraviolet-visible (UV-vis) spectroscopy, and electronic structure calculations. Our results show a series of stages in the ion pairing of the divalent cation, Cu(II), including the contact ion pairing of Cu2+ with multiple Cl- ligands to form various CuCln(2-n) polyanions, as well as the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM+ cation. ion-pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen-bond network in [EMIM]Cl-water mixtures. The CuCl42- species dominates in the [EMIM]Cl solvent, and calculations along with spectroscopy show that its geometry distorts to C-2 symmetry compared to Did in the gas phase. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.
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