Cation Effect on the Electrochemical Platinum Dissolution

作     者：Kim, Haesol Kim, Minho M. Cho, Junsic Lee, Seunghoon Kim, Dong Hyun Shin, Seung-Jae Utsunomiya, Tomohiko Goddard III, William A. Katayama, Yu Kim, Hyungjun Choi, Chang Hyuck 

作者机构：Pohang Univ Sci & Technol Dept Chem Pohang 37673 South Korea Korea Adv Inst Sci & Technol Dept Chem Daejeon 34141 South Korea Ulsan Natl Inst Sci & Technol Sch Energy & Chem Engn Ulsan 44919 South Korea Osaka Univ SANKEN Ibaraki 5670047 Japan Osaka Univ Dept Engn Suita 5650871 Japan CALTECH Mat & Proc Simulat Ctr Pasadena CA 91125 USA Yonsei Univ Inst Convergence Res & Educ Adv Technol Seoul 03722 South Korea 

出 版 物：《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 (J. Am. Chem. Soc.)

年 卷 期：2025年第147卷第5期

页      面：4667-4674页

核心收录：

学科分类：07[理学] 0703[理学-化学] 

基　　金：National Research Foundation of Korea [SSTF-BA2101-08] Samsung Science and Technology Foundation [RS-2024-00406517, RS-2024-00450102, RS-2024-00405261] National Research Foundation of Korea (NRF) - Ministry of Science and ICT (MSIT) 

主　　题：Rough paths Signatures Strong approximations Berry-Esseen estimates alpha Phi- and psi-mixing Shifts Dynamical systems Phi- and psi-mixing Stationary process Shifts Dynamical systems 

摘      要：Ensuring the stability of electrocatalysts is paramount to the success of electrochemical energy conversion devices. Degradation is a fundamental process involving the release of positively charged metal ions into the electric double layer (EDL) and their subsequent diffusion into the bulk electrolyte. However, despite its vital importance in achieving prolonged electrocatalysis, the underlying causality of catalyst dissolution with the EDL structure remains largely unknown. Here, we show that electrochemical Pt dissolution is strongly influenced by the identity of the alkali metal cation (AM(+)) in the electrolyte. By monitoring Pt dissolution in real-time, we found a trend of reduced Pt leaching in the sequence Li+ Na+ K+ Cs+. Our computational predictions suggest that interfacial OH- concentration plays a pivotal role in Pt dissolution, where OH- facilitates the outward diffusion of dissolved Pt ions into the bulk electrolyte by neutralizing the Ptz+ species, thereby screening the migration force for their redeposition. Combined with this theoretical result, we verify a strong correlation between the amount of dissolved Pt and the hydrolysis pK(a) or acidity of AM(+), indicating that the AM(+) identity determines the local OH- concentration and thereby modifies the amount of Pt dissolution. Our results underscore the need to tune the EDL structure to achieve durable electrocatalysis, a promising area for future research.