Redox characteristics variations in the cation-ordered perovskite oxides BaLnMn2O5+d (Ln = Y, Gd, Nd, and La) and Ca2Al1-xGaxMnO5+d (0 =< x =< 1)
Redox characteristics variations in the cation-ordered perovskite oxides BaLnMn2O5+d (Ln = Y, Gd, Nd, and La) and Ca2Al1-xGaxMnO5+d (0 =< x =< 1)
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阳离子有序钙钛矿氧化物 BaLnMn2O5 d (Ln = Y、Gd、Nd 和 La) 和 Ca2Al1-xGaxMnO5 d (0 =< x =< 1) 的氧化还原特性变化
DOI：
10.1039/c4dt03863k
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发表时间：
2015
影响因子：
4
通讯作者：
and S. Kikkawa
中科院分区：
文献类型：
--
作者：
T. Motohashi;M. Kimura;T. Inayoshi;T. Ueda;Y. Masubuchi;and S. Kikkawa
合成了BaLnMn2O5+δ (Ln = Y, Gd, Nd, La)和Ca2Al1−xGaxMnO5+δ(0≤x≤1)两个系列锰基储氧材料，并对其进行了表征，以阐明阳离子取代对这些材料吸氧/释放行为的影响。热重数据表明，在活性位点附近的等价取代对氧气的吸入/释放是非常有效的。对于BaLnMn2O5+δ，具有较大Ln离子的全还原δ≈0产物在流动的O2气体中从较低的温度开始吸氧，导致起始温度与Ln3+离子半径之间存在系统关系。此外，在700℃时的δ与P（O2）曲线显示出一个系统的趋势：Ln3+离子尺寸越大，ln产物的氧含量也越大。另一方面，对于Ca2Al1−xGaxMnO5+δ，温度诱导的氧气吸入/释放特性似乎受到Ga- For - al取代的影响，其中氧气释放（加热时）和氧气吸入（冷却时）的起始温度随着Ga含量的增加而降低(x)。
Two series of manganese-based oxygen storage materials, BaLnMn2O5+δ (Ln = Y, Gd, Nd, and La) and Ca2Al1−xGaxMnO5+δ (0 ≤ x ≤ 1), were synthesized and characterized to clarify cationic substitution effects on the oxygen intake/release behaviors of these materials. The thermogravimetric data revealed that the isovalent substitutions neighboring the active sites for oxygen intake/release are very effective. For BaLnMn2O5+δ, fully-reduced δ ≈ 0 products with larger Ln ions showed oxygen intake starting at lower temperatures in flowing O2 gas, resulting in a systematic relationship between the onset temperature and the ionic radius of Ln3+. Furthermore, the δ vs. P(O2) plots at 700 °C indicated a systematic trend: the larger the ionic size of Ln3+ is, the larger oxygen contents the Ln-products exhibit. For Ca2Al1−xGaxMnO5+δ, on the other hand, the temperature-induced oxygen intake/release characteristics appeared to be influenced by Ga-for-Al substitution, where the onset temperatures of oxygen release (upon heating) and oxygen intake (upon cooling) are decreased with the increasing Ga content (x).