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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\u2013driven catalysis at single-molecule and subparticle level, which is able to help the design of highly efficient defect-based catalysts.<\/jats:p>","DOI":"10.1073\/pnas.2317205121","type":"journal-article","created":{"date-parts":[[2024,5,22]],"date-time":"2024-05-22T13:45:00Z","timestamp":1716385500000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":19,"title":["Revealing operando surface defect\u2013dependent electrocatalytic performance of Pt at the subparticle level"],"prefix":"10.1073","volume":"121","author":[{"given":"Yi","family":"Xiao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Electroanalytical Chemistry and Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People\u2019s Republic of China"},{"name":"School of Applied Chemistry and 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