Revealing operando surface defect-dependent electrocatalytic performance of Pt at the subparticle level

• 成果类型: Article
• 署名作者: Xiao, Yi; Guo, Zhichao; Cao, Jing; Song, Ping; Yang, Bo; Xu, Weilin
• 署名单位: Chinese Academy of Sciences; Changchun Institute of Applied Chemistry, CAS; Chinese Academy of Sciences; Changchun Institute of Applied Chemistry, CAS; Chinese Academy of Sciences; University of Science & Technology of China, CAS; ShanghaiTech University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-12364
• DOI: 10.1073/pnas.2317205121
• 发表日期: 2024-05-20
• 关键词: methanol fuel-cells; single-molecule; co2 hydrogenation; activation-energies; oxidation; MODEL; water; electrooxidation; nanostructures; mechanism

摘要

Understanding the operando defect-tuning performance of catalysts is critical to establish an accurate structure-activity relationship of a catalyst. Here, with the tool of single - molecule super - resolution fluorescence microscopy, by imaging intermediate CO formation/oxidation during the methanol oxidation reaction process on individual defective Pt nanotubes, we reveal that the fresh Pt ends with more defects are more active and anti - CO poisoning than fresh center areas with less defects, while such difference could be reversed after catalysis - induced step - by - step creation of more defects on the Pt surface. Further experimental results reveal an operando volcano relationship between the catalytic performance (activity and anti - CO ability) and the fine - tuned defect density. Systematic DFT calculations indicate that such an operando volcano relationship could be attributed to the defect - dependent transition state free energy and the accelerated surface reconstructing of defects or Pt - atom moving driven by the adsorption of the CO intermediate. These insights deepen our understanding to the operando defect-driven catalysis at single - molecule and subparticle level, which is able to help the design of efficient defect - based