Topochemical Synthesis and Formation Mechanism of Garnet Multimetal Fluorides

Kumar, K and Thapliyal, P and Bhutani, D and Rubu, R and Debadatta, SK and Jain, SK and Senguttuvan, P (2024) Topochemical Synthesis and Formation Mechanism of Garnet Multimetal Fluorides. In: ACS Materials Letters . pp. 5285-5291.

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Abstract

The synthesis of multimetal fluorides (MMFs) is challenged by the usage of toxic fluoride precursors and their thermodynamic instability at higher temperatures. Here, we demonstrate a new topochemical reaction pathway to tailor garnet-type single- and multimetal fluorides from double perovskite (DP) hosts. Our combined X-ray diffraction, Fourier-transformed infrared, and nuclear magnetic spectroscopic techniques reveal the transformation pathway as DP-(NH4)3(M/M�)3+F6 to DP-(NH4)2(Na/Li)(M/M�)3+F6 to garnet-Na3Li3(M/M�)2F12 ((M/M�)3+ = Al3+, Fe3+, Cr3+ and V3+) through ion-exchange reaction between NH4+ and Li+/Na+ ions. The garnet MMF-Na3Li3(Fe0.33Cr0.33V0.33)2F12 catalyst displays ultralow overpotential (η500 of 245 mV) with higher durability. © 2024 American Chemical Society.

Item Type:	Journal Article
Publication:	ACS Materials Letters
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to the Publisher.
Keywords:	Chromium compounds; Fourier transform infrared spectroscopy; Fourier transforms; Garnets; Nuclear magnetic resonance spectroscopy, Combined X ray diffraction; Double perovskites; Formation mechanism; Highest temperature; Multi-metals; Reaction pathways; Synthesis mechanism; Thermodynamic instability; Topochemical; Topochemical reaction, Perovskite
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	09 Dec 2024 17:16
Last Modified:	09 Dec 2024 17:16
URI:	http://eprints.iisc.ac.in/id/eprint/87070

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