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Cation Driven Charge Transfer in (Co, Fe) Prussian Blues
Author(s) -
Sheu HwoShuenn,
Jen ShihHui,
Kang TingWei,
Jang LingYun,
Lee JyhFu
Publication year - 2002
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200200116
Subject(s) - prussian blue , chemistry , valence (chemistry) , cobalt , absorption spectroscopy , inorganic chemistry , analytical chemistry (journal) , alkali metal , crystallography , electrochemistry , electrode , physics , organic chemistry , quantum mechanics , chromatography
The charge transfer between Cobalt and Iron ions in a series of (Co, Fe) Prussian blues has been investigated by synchrotron X‐ray absorption spectroscopy and powder diffraction. (Co, Fe) Prussian blues, A x Co y [Fe(CN) 6 ]‐nH 2 O where A = Li, Na, K, Rb and Cs, were prepared by dropwise mixing method. X‐ray absorption near edge spectra showed that cobalt was in a higher oxidation state when the interstitial alkali cation changed from Li, Na, to K, Rb, Cs. At the same time, the valence of Fe shifted from 3+ to 2+. The cation driven charge transfer ability follows the order of Li ≈ Na < K < Rb ≈ Cs. A similar trend was also found when the KCl concentration was increased during the synthesis of K‐containing Prussian blue. The higher the concentration of KCl, the more Fe 2+ ‐CN‐Co 3+ fragment in the (Co, Fe) Prussian blue, and hence the higher efficiency for photo‐induced magnetization. The Co‐N distance in Prussian blue became shorter, about 0.15 Å in Co 2+ salt compared to Co 3+ salt, and the unit cell dimension was reduced about 0.3 Å as well.