4.8 Article

Dehydration of Electrochemically Protonated Oxide: SrCoO2 with Square Spin Tubes

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 42, Pages 17517-17525

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c07043

Keywords

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Funding

  1. CREST [JPMJCR20R2, JPMJCR1421]
  2. Japan Society for the Promotion of Science (JSPS) [JPJSCCA20200004]
  3. JSPS
  4. JSPS [JP21H05561]
  5. Research Foundation for the Electrotechnology of Chubu
  6. Murata Science Foundation
  7. National Supercomputer Center in Tianjin through National Natural Science Foundation of China [11874223, 51871121]
  8. [JP16H06438]
  9. [JP16H06439]
  10. [19F19334]
  11. [JP21K18196]

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The study demonstrates that highly reduced oxides, such as SrCoO2, can be obtained through electrochemical protonation combined with thermal dehydration, resulting in novel crystal structures. This method expands the exploration of novel functional oxides by widening the possibilities for research.
Controlling oxygen deficiencies is essential for the development of novel chemical and physical properties such as high-Tc superconductivity and low-dimensional magnetic phenomena. Among reduction methods, topochemical reactions using metal hydrides (e.g., CaH2) are known as the most powerful method to obtain highly reduced oxides including Nd0.8Sr0.2NiO2 superconductor, though there are some limitations such as competition with oxyhydrides. Here we demonstrate that electrochemical protonation combined with thermal dehydration can yield highly reduced oxides: SrCoO2.5 thin films are converted to SrCoO2 by dehydration of HSrCoO2.5 at 350 degrees C. SrCoO2 forms square (or four-legged) spin tubes composed of tetrahedra, in contrast to the conventional infinite-layer structure. Detailed analyses suggest the importance of the destabilization of the SrCoO2.5 precursor by electrochemical protonation that can greatly alter reaction energy landscape and its gradual dehydration (H1-xSrCoO2.5-x/2) for the SrCoO2 formation. Given the applicability of electrochemical protonation to a variety of transition metal oxides, this simple process widens possibilities to explore novel functional oxides.

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