Topochemical Synthesis and Formation Mechanism of Garnet Multimetal Fluorides

IF 8.7 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2024-10-31 DOI:10.1021/acsmaterialslett.4c0169010.1021/acsmaterialslett.4c01690

Keshav Kumar, Prabhat Thapliyal, Divya Bhutani, Rinya Rubu, Shubham Kumar Debadatta, Sheetal Kumar Jain and Premkumar Senguttuvan*,

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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(Fe_0.33Cr_0.33V_0.33)₂F₁₂ catalyst displays ultralow overpotential (η₅₀₀ of 245 mV) with higher durability.

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石榴石多金属氟化物的拓扑化学合成及形成机理

多金属氟化物（MMFs）的合成受到有毒氟前体的使用及其在高温下的热力学不稳定性的挑战。在这里，我们展示了一种新的拓扑化学反应途径，从双钙钛矿（DP）宿主中定制石榴石型单金属和多金属氟化物。结合x射线衍射、傅里叶变换红外和核磁波谱技术，揭示了通过NH4+和Li+/Na+离子之间的离子交换反应，DP-(NH4)3（M/M′）3+F6转化为DP-(NH4)2(Na/Li)（M/M′）3+F6转化为石榴石na3li3 （M/M′）2F12 （（M/M′）3+ = Al3+, Fe3+， Cr3+和V3+）。石榴石MMF-Na3Li3(Fe0.33Cr0.33V0.33)2F12催化剂具有超低过电位（η500为245 mV）和较高的耐久性。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.