Solvation Effect-Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts

IF 16.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2024-10-16 DOI:10.1002/anie.202418248

Shangheng Liu, Xiaocan Wang, Wei-Hsiang Huang, Qiugen Zhang, Jiajia Han, Yingtian Zhang, Chih-Wen Pao, Zhiwei Hu, Yong Xu, Xiaoqing Huang

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Abstract

Cation exchange (CE) reaction is a classical synthesis method for creating complex structures. A lock of study on intrinsic mechanism limits its understanding and practical application. Using X-ray absorption spectroscopy, we observed that the evolution from Ru−Cl to Ru−O/OH occurs during the CE between K2RuCl6 and CoSn(OH)6 in aqueous solution, while CE between K2PtCl6 and CoSn(OH)6 is inhibited due to the failure of structural evolution from Pt−Cl to Pt−O/OH. Theoretical simulations imply that the interaction between Ru−O and CoSn(OH)6 with Co vacancy (CoVCoSn(OH)6) endows the electron transfer, as a result of strengthened adsorption on CoVCoSn(OH)6. Moreover, this mechanism is validated for CE between K2RuCl6 and ASn(OH)6 (A = Mg, Ca, Mn, Co, Cu, Zn), and CE between K2PdCl6/Na3RhCl6/K2IrCl6 and CoSn(OH)6. Impressively, the Pt-free CoRuSn(OH)x produced via CE displays a mass activity and a power density of 15.0 A mgRu−1 and 11.6 W mgRu−1, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mgRu+Pt−1 and 9.0 W mgRu+Pt−1). This work, for the first time, reveals the intrinsic mechanism of CE as structural evolution of target ion breaking through the traditional classic etch-adsorption mechanism and will promote fundamental research and practical application in various fields.

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溶解效应决定的高效多组分纳米催化剂阳离子交换反应机理

阳离子交换（CE）反应是创造复杂结构的经典合成方法。对其内在机理的研究不足限制了对它的理解和实际应用。利用 X 射线吸收光谱，我们观察到 K2RuCl6 与 CoSn(OH)6 在水溶液中发生阳离子交换反应时，Ru-Cl 向 Ru-O/OH 演化，而 K2PtCl6 与 CoSn(OH)6 发生阳离子交换反应时，由于 Pt-Cl 向 Pt-O/OH 的结构演化失败而受到抑制。理论模拟表明，Ru-O 和 CoSn(OH)6 与 Co 空位（CoVCoSn(OH)6）之间的相互作用赋予了电子转移能力，这是 CoVCoSn(OH)6 吸附能力增强的结果。此外，K2RuCl6 和 ASn(OH)6（A = Mg、Ca、Mn、Co、Cu、Zn）之间的 CE 以及 K2PdCl6/Na3RhCl6/K2IrCl6 和 CoSn(OH)6 之间的 CE 也验证了这一机制。令人印象深刻的是，在阴离子交换膜燃料电池（AEMFC）中，通过 CE 生产的无铂 CoRuSn(OH)x 的质量活性和功率密度分别达到 15.0 A mgRu-1 和 11.6 W mgRu-1，超过了商用 PtRu/C 的值（11.8 A mgRu+Pt-1 和 9.0 W mgRu+Pt-1）。这项工作首次揭示了 CE 的内在机理，即目标离子的结构演化突破了传统的经典蚀刻-吸附机理，将促进各领域的基础研究和实际应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

CiteScore

26.60

自引率

6.60%

发文量

3549

审稿时长

1.5 months

期刊介绍： Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.