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Gold atomic clusters extracting the valence electrons to shield the carbon monoxide passivation on near-monolayer core–shell nanocatalysts in methanol oxidation reactions

Tsan‐Yao ChenDepartment of Engineering and System ScienceHong Dao LiDepartment of PhysicsGuo-Wei LeeDepartment of PhysicsPo‐Chun HuangDepartment of Engineering and System SciencePo‐Wei YangDepartment of Engineering and System ScienceYuting LiuDepartment of Environmental Science and EngineeringYen‐Fa LiaoHsinchu 30013Horng‐Tay JengDepartment of PhysicsDeng-Sung LinDepartment of PhysicsTsang‐Lang LinDepartment of Engineering and System Science
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Atomic-scale gold clusters were intercalated at the inter-facet corner sites of Pt-shell Ru-core nanocatalysts with near-monolayer shell thickness. We demonstrated that these unique clusters could serve as a drain of valence electrons in the kink region of the core-shell heterojunction. As jointly revealed by density functional theory calculations and valence band spectra, these Au clusters extract core-level electrons to the valence band. They prevent corrosion due to protonation and enhance the tolerance of CO by increasing the electronegativity at the outermost surface of the NCs during the methanol oxidation reaction (MOR). In these circumstances, the retained current density of Pt-shell Ru-core NCs is doubled in a long-term (2 hours) MOR at a fixed voltage (0.5 V vs. SCE) by intercalating these sub-nanometer gold clusters. Such novel structural confinement provides a possible strategy for developing direct-methanol fuel cell (DMFC) modules with high power and stability.

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