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However, its broader application is limited by the high working potential and the low DMC selectivity accompanied with severe methanol self\u2010oxidation. Herein, our theoretical analysis of the intermediate adsorption interactions on both Pd<jats:sup>0<\/jats:sup> and Pd<jats:sup>4+<\/jats:sup> surfaces revealed that inevitable reconstruction of Pd surface under strongly oxidative potential diminishes its CO adsorption capacity, thus damaging the DMC formation. Further theoretical modeling indicates that doping Pd with Cu not only stabilizes low\u2010valence Pd in oxidative environments but also lowers the overall energy barrier for DMC formation. Guided by this insight, we developed a facile two\u2010step thermal shock method to prepare PdCu alloy electrocatalysts for DMC. Remarkably, the predicted Pd<jats:sub>3<\/jats:sub>Cu demonstrated the highest DMC selectivity among existing Pd\u2010based electrocatalysts, reaching a peaked DMC selectivity of 93\u2009% at 1.0\u2005V versus Ag\/AgCl electrode. (Quasi) <jats:italic>in situ<\/jats:italic> spectra investigations further confirmed the predicted dual role of Cu dopant in promoting Pd\u2010catalyzed DMC formation.<\/jats:p>","DOI":"10.1002\/anie.202401311","type":"journal-article","created":{"date-parts":[[2024,4,12]],"date-time":"2024-04-12T08:09:40Z","timestamp":1712909380000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["Stabilization of Pd<sup>0<\/sup> by Cu Alloying: Theory\u2010Guided Design of Pd<sub>3<\/sub>Cu Electrocatalyst for Anodic Methanol Carbonylation"],"prefix":"10.1002","volume":"63","author":[{"given":"Yunru","family":"Shi","sequence":"first","affiliation":[{"name":"State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP) Chinese Academy of Sciences  Lanzhou 730000 China"},{"name":"University of Chinese Academy 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