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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >New insight into the vibrational behavior of nickel hydroxide and oxyhydroxide using inelastic neutron scattering, far/mid-infrared, and Raman spectroscopies
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New insight into the vibrational behavior of nickel hydroxide and oxyhydroxide using inelastic neutron scattering, far/mid-infrared, and Raman spectroscopies

机译：使用非弹性中子散射，远/中红外和拉曼光谱学对氢氧化镍和羟基氧化氢的振动行为的新见解

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摘要

The electrochemical properties of beta-type nickel (oxy)hydroxides Ni(OH)(2) and NiO(OH) are known to depend significantly, on their structural features. In this work, these features are investigated by means of inelastic neutron scattering and infrared and Raman spectroscopies. Our experiments probe both inter- and intramolecular (40-4000 cm(-1)) vibrational ranges and particular attention is paid to the low-frequency (40-300 cm(-1)) domain, where new features are observed. Namely, the presence of an IR active mode at around 130 cm(-1), characteristic of the oxidized beta-NiO(OH) phase, is observed for the first time. The effects of temperature (10-300 K) and deuteration are also measured in order to provide deeper insight into the nature of the vibrational states. A detailed comparison of all of the collected data allows us to propose a new assignment of the vibrational features observed in both beta-Ni(OH)(2) and beta-NiO(OH) and to quantify the proton dynamic relevance on the vibrational modes. We show that the interlayer interactions are mostly electrostatic and, hence, do not involve hydrogen bonding. We also point out that, in the oxidized beta-phase, protons cannot be localized so that they can be considered as fully labile. To sum up, this investigation emphasizes that proton delocalization and crystalline disorder, which arise concomitantly upon oxidation, are the key factors that explain the evolution of the vibrational features observed between the oxidized and reduced beta-type forms.
机译：已知β型氢氧化镍（Ni）（2）和NiO（OH）的电化学性质在很大程度上取决于其结构特征。在这项工作中，这些特征是通过非弹性中子散射，红外和拉曼光谱学研究的。我们的实验同时探查了分子间和分子内（40-4000 cm（-1））的振动范围，并特别注意了低频（40-300 cm（-1））域，在其中观察到了新的特征。即，首次观察到在约130 cm（-1）处存在IR活性模式，这是氧化的β-NiO（OH）相的特征。还测量了温度（10-300 K）和氘的影响，以便更深入地了解振动状态的本质。通过对所有收集到的数据进行详细比较，我们可以对在β-Ni（OH）（2）和β-NiO（OH）中观察到的振动特征提出新的分配，并量化质子在振动模式下的动态相关性。我们表明，层间相互作用主要是静电的，因此，不涉及氢键。我们还指出，在氧化的β相中，质子无法定位，因此可以认为它们完全不稳定。总而言之，这项研究强调质子离位和晶体紊乱（伴随氧化而出现）是解释在氧化和还原的β型形式之间观察到的振动特征演变的关键因素。

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