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Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy

Adak, S.; Hartl, M. LU ; Daemen, Luc; Fohtung, E. and Nakotte, H. (2017) In Journal of Electron Spectroscopy and Related Phenomena 214. p.8-19
Abstract

There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates MII3[AIII(CN)6]2*nH2O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), MII2[FeII(CN)6]2*nH2O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III)... (More)

There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates MII3[AIII(CN)6]2*nH2O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), MII2[FeII(CN)6]2*nH2O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe1-xCox)3[BIII(CN)6]2·nH2O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Hexacyanometallates, Oxidation states, Prussian blue analogs, XANES
in
Journal of Electron Spectroscopy and Related Phenomena
volume
214
pages
12 pages
publisher
Elsevier
external identifiers
  • scopus:85006380287
  • wos:000392037700002
ISSN
0368-2048
DOI
10.1016/j.elspec.2016.11.011
language
English
LU publication?
yes
id
d125eb6f-22d8-4e83-8ad1-9764e19c7fb1
date added to LUP
2017-03-24 12:05:49
date last changed
2017-09-18 11:34:09
@article{d125eb6f-22d8-4e83-8ad1-9764e19c7fb1,
  abstract     = {<p>There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates M<sup>II</sup><sub>3</sub>[A<sup>III</sup>(CN)<sub>6</sub>]<sub>2*</sub>nH<sub>2</sub>O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), M<sup>II</sup><sub>2</sub>[Fe<sup>II</sup>(CN)<sub>6</sub>]<sub>2*</sub>nH<sub>2</sub>O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe<sub>1-x</sub>Co<sub>x</sub>)<sub>3</sub>[B<sup>III</sup>(CN)<sub>6</sub>]<sub>2</sub>·nH<sub>2</sub>O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.</p>},
  author       = {Adak, S. and Hartl, M. and Daemen, Luc and Fohtung, E. and Nakotte, H.},
  issn         = {0368-2048},
  keyword      = {Hexacyanometallates,Oxidation states,Prussian blue analogs,XANES},
  language     = {eng},
  month        = {01},
  pages        = {8--19},
  publisher    = {Elsevier},
  series       = {Journal of Electron Spectroscopy and Related Phenomena},
  title        = {Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy},
  url          = {http://dx.doi.org/10.1016/j.elspec.2016.11.011},
  volume       = {214},
  year         = {2017},
}