Solvation Effect‐Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts
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 K<sub>2</sub>RuCl<sub>6</sub> and CoSn(OH)<sub>6</sub> in aqueous solution, while CE between K<sub>2</sub>PtCl<sub>6</sub> and CoSn(OH)<sub>6</sub> 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)<sub>6</sub> with Co vacancy (CoV<sub>Co</sub>Sn(OH)<sub>6</sub>) endows the electron transfer, as a result of strengthened adsorption on CoV<sub>Co</sub>Sn(OH)<sub>6</sub>. Moreover, this mechanism is validated for CE between K<sub>2</sub>RuCl<sub>6</sub> and ASn(OH)<sub>6</sub> (A=Mg, Ca, Mn, Co, Cu, Zn), and CE between K<sub>2</sub>PdCl<sub>6</sub>/Na<sub>3</sub>RhCl<sub>6</sub>/K<sub>2</sub>IrCl<sub>6</sub> and CoSn(OH)<sub>6</sub>. Impressively, the Pt-free CoRuSn(OH)<sub>x</sub> produced via CE displays a mass activity and a power density of 15.0 A mg<sub>Ru</sub> <sup>-1</sup> and 11.6 W mg<sub>Ru</sub> <sup>-1</sup>, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mg<sub>Ru+Pt</sub> <sup>-1</sup> and 9.0 W mg<sub>Ru+Pt</sub> <sup>-1</sup>). 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.
Authors
- Jiajia Han (ORCID: https://orcid.org/0000-0002-2642-0252)
- Zhiwei Hu (ORCID: https://orcid.org/0000-0003-0324-2227)
- Yong Xu (ORCID: https://orcid.org/0000-0003-0515-7181)
- Yingtian Zhang (ORCID: https://orcid.org/0009-0007-7220-8571)
- Shangheng Liu
- Xiaocan Wang
- Chih‐Wen Pao (ORCID: https://orcid.org/0000-0001-7681-4391)
- Xiaoqing Huang (ORCID: https://orcid.org/0000-0003-3219-4316)
- Wei‐Hsiang Huang (ORCID: https://orcid.org/0000-0001-9503-0373)
- Qiu Gen Zhang (ORCID: https://orcid.org/0000-0003-0998-1506)
Institutions
- Tianjin University of Technology (CN)
- Tianjin University (CN)
- Xiamen University (CN)
- Chinese Academy of Sciences (CN)
- Suzhou Institute of Nano-tech and Nano-bionics (CN)
- National Synchrotron Radiation Research Center (TW)
- Max Planck Institute for Chemical Physics of Solids (DE)
- Tan Kah Kee Innovation Laboratory (CN)
- Collaborative Innovation Center of Chemistry for Energy Materials (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-10-16
- DOI
- https://doi.org/10.1002/anie.202418248
- Citations
- 4
- Primary Topic
- Electrochemical Analysis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.69
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Guangdong Province for Distinguished Young Scholars