Evaluating chemical bonding in dioxides for the development of metal-oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides.
Evaluating chemical bonding in dioxides for the development of metal-oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides.
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DOI：
10.1039/c8cp04652b
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发表时间：
2019-01
期刊：
影响因子：
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通讯作者：
P. Radjenovic;L. Hardwick
中科院分区：
文献类型：
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作者：
P. Radjenovic;L. Hardwick
二氧化物（二氧化基 (O2+)、双氧 (O2)、超氧化物 (O2˙-) 和过氧化物 (O22-)）具有巨大的生物、化学和环境重要性。准确检测和测量原位或原位化学键和配位变化强度的能力对于评估其化学性质极为有益，这在最近的金属氧电池领域尤为重要，其中了解O2˙-中间体的反应性对于开发更稳定的电解质至关重要。对众多（>200）双氧物质的振动拉曼和红外光谱带进行荟萃分析，用于解释直接化学环境对 O-O 键的影响。随后，二氧化物振动谱带在经验上与键电子密度和其他基本键特性直接相关，具有令人惊讶的高精确度，允许通过实验光谱观察简单地估计每个特性。还可以阐明有关还原氧物质与其化学环境之间的二次相互作用强度的重要化学信息，这提供了一种确定离子对相邻反离子施加的吸引力强度的便捷方法。
Dioxides (dioxygenyl (O2+), dioxygen (O2), superoxide (O2˙-) and peroxide (O22-)) are of immense biological, chemical and environmental importance. The ability to accurately detect and measure the changing strength of their chemical bonding and coordination in situ or operando is extremely beneficial in order to evaluate their chemical properties, this has been particularly important recently in the field of metal-oxygen batteries, where understanding the reactivity of the O2˙- intermediate is crucial in the development of more stable electrolytes. Meta-analysis of the collated vibrational Raman and IR spectral bands of numerous (>200) dioxygen species was used to interpret the effect that the immediate chemical environment has on the O-O bond. Subsequently, the dioxide vibrational spectral bands were empirically related directly with the bond electron density and other fundamental bond properties, with surprisingly high accuracy, allowing each property to be estimated, simply, from experimental spectroscopic observations. Important chemical information about the strength of secondary interactions between reduced oxygen species and its chemical environment can be also elucidated which provides a convenient method for determining the attractive strength an ion exerts over neighbouring counter ions.