Persistence and Amalgamation Types of CN Stretching Mode in Oxidation Process of Prussian Blue Analogues
Persistence and Amalgamation Types of CN Stretching Mode in Oxidation Process of Prussian Blue Analogues
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DOI：
10.7566/jpsj.89.064708
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发表时间：
2020-06-15
影响因子：
1.7
通讯作者：
Moritomo, Yutaka
中科院分区：
文献类型：
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作者：
Moriya, Toshiaki;Shibata, Takayuki;Moritomo, Yutaka
普鲁士蓝类似物（PBAs）具有氰基桥联的三维过渡金属网络结构，-M-NC-Fe-CN-M-NC-Fe-CN-M-（M = Co和Mn）。在这里，通过原位红外（IR）光谱，我们研究了氧化CN伸缩模式的影响。CN伸缩模式显示出持久性或合并行为，这取决于还原态和氧化态之间的声子能量（（h）相对于棒Ω（CN））的差异（Delta），例如，M2+-NC-Fe ~（2+）和M2+-NC-Fe ~（2+）。我们发现氰铁（[Fe ~（2+）（CN）]（4-））的带宽（W ≥ 39 cm ~（-1））大于氰铁（[Fe ~（3+）（CN）]（3-））的带宽（W ≥ 23 cm ~（-1））。较大的W在氰亚铁被解释在氰亚铁中CN的较强的极化。
Prussian blue analogues (PBAs) shows a cyano-bridged three-dimensional (3D) transition metal network, -M-NC-Fe-CN-M-NC-Fe-CN-M- (M = Co and Mn). Here, by in situ infrared (IR) spectroscopy, we investigated effect of the oxidation on the CN stretching mode. The CN stretching mode shows persistence or amalgamation behavior depending on the difference (Delta) in the phonon energies ((h) over bar omega(CN)) between the reduced and oxidized states, e.g., M2+-NC -Fe2+ and M2+-NC-Fe2+. We found that the band width (W >= 39 cm(-1)) in ferrocyan ([Fe2+(CN)](4-)] is larger than that (= 23 cm(-1)) in ferricyan ([Fe3+(CN)](3-)). The larger W in ferrocyan is interpreted in terms of the stronger polarization of CN in ferrocyan.