Ionic control of mixed-anion compounds and reduced oxides using electric field

利用电场对混合阴离子化合物和还原氧化物进行离子控制

• 批准号: 19F19334
• 负责人: 陰山 洋
• 金额: $ 1.47万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2019
• 资助国家: 日本
• 起止时间: 2019-10-11 至 2022-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19F19334/
• 关键词: Ionic manipulation; Electric-field control; Phase transition; Topochemical reaction; Proton insertion; Complex oxide; Mixed-anions; Thin film

Our work shows that using the electrochemical protonation and associated dehydration reaction paves out a novel route to explore reduced metal oxides. The dehydration is also simple but effective. It is quite similar as the general dehydration occurs in ATP or alcohol synthesis, where the bonding oxygen is removed and new bonding and structure are formed. However, the electric-field provides additional energy to weaken the metal-oxygen hybridization. Thus, the lattice oxygen can be easily released from the system under heating, when these oxygen ions cannot be removed by other methods.The obtained SrCoO2 exhibits unique 4-legged spin-tube structure, which cannot be obtained by well-known reduction reactions. Considering the electrochemical protonation is well explored in many oxides, large number of precursors can be considered to explore their products after dehydration. Even for known oxyhydride, electrochemical protonation might further reduce these compounds and H2 releasing instead of H2O can be expected. More importantly, the proton injection/dehydration could be expanded to all types of materials and this will eventually reveal large number of undiscovered structures and associated exotic properties.In the final fiscal year of this funding, our results were accepted by Journal of the American Chemical Society (J. Am. Chem. Soc. 2021, 143, 42, 17517-17525). The related results will be also presented in JSAP 69th conference in 2022 Spring.

我们的工作表明，利用电化学质子化和相关的脱水反应为探索还原金属氧化物开辟了一条新的途径。脱水也很简单，但很有效。这与ATP或醇合成中发生的一般脱水非常相似，其中键合氧被去除，并形成新的键合和结构。然而，电场提供了额外的能量来削弱金属-氧杂化。因此，晶格氧可以很容易地从系统中释放出来，当这些氧离子不能通过其他方法去除时，所获得的SrCoO 2具有独特的四脚自旋管结构，这是不能通过已知的还原反应获得的。考虑到电化学质子化在许多氧化物中被很好地探索，可以考虑大量的前体来探索它们脱水后的产物。即使对于已知的氢氧化物，电化学质子化也可能进一步还原这些化合物，并且可以预期释放H2而不是H2O。更重要的是，质子注入/脱水可以扩展到所有类型的材料，这将最终揭示大量未发现的结构和相关的奇异性质。2021，143，42，17517-17525）。相关成果也将在2022年春季的JSAP第69届会议上发表。