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Redox-Neutral Interstitial Hydride Incorporation in Ruddlesden-Popper Oxides
Daichi Kato1, Shuhei Ueda1, Tong Zhu1
1Department of Chemical Science and Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan.
Researchers developed a new redox-neutral method to create perovskite oxyhydrides by exchanging oxygen for hydride anions. This expands the range of functional materials, enabling exploration of properties like ion conductivity.
Area of Science:
- Materials Science
- Solid-State Chemistry
- Inorganic Chemistry
Background:
- Perovskite oxyhydrides offer diverse functionalities but are limited by synthesis methods relying on cation reduction.
- Conventional topochemical hydridation restricts the compositional space of these materials.
Purpose of the Study:
- To introduce a novel redox-neutral topochemical route for synthesizing Ruddlesden-Popper (RP) oxyhydrides.
- To investigate the incorporation and structural effects of hydride anions in RP frameworks.
Main Methods:
- Employed an O2-/2H- exchange reaction for topochemical hydride insertion into rock-salt layers.
- Synthesized SrLaScO4-x/2Hx and ALa2Sc2O7-x/2Hx (A = Sr, Ba) using the redox-stable Sc3+.
Main Results:
- Achieved systematic hydride incorporation, yielding Sr phases (x ∼ 2.0) with unusual octahedral tilting and Ba phases (x ∼ 3.2) with higher hydride content.
- Demonstrated site-selective hydride occupation in Sr phases governed by electrostatic interactions.
- Correlated hydride incorporation levels with interstitial site geometry and the Goldschmidt tolerance factor in Ba phases.
Conclusions:
- Established a versatile redox-neutral pathway for interstitial hydride incorporation in RP oxyhydrides.
- Revealed a structural design principle for controlling hydride occupancy based on framework geometry.
- Opened avenues for exploring new functional properties, including hydride-ion conductivity and hybrid improper ferroelectricity.
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