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The control of multimetallic ensembles at the atomic-level is challenging, especially for high-entropy alloys (HEAs) possessing five or more elements. Herein, the one-pot synthesis of hexagonal-close-packed (hcp) PtRhBiSnSb high-entropy intermetallic (HEI) nanoplates with intrinsically isolated Pt, Rh, Bi, Sn, and Sb atoms is reported, to boost the electrochemical oxidation of liquid fuels. Taking advantage of these combined five metals, the well-defined PtRhBiSnSb HEI nanoplates exhibit a remarkable mass activity of 19.529, 15.558, and 7.535 A mg-1 Pt+Rh toward the electrooxidation of methanol, ethanol, and glycerol in alkaline electrolytes, respectively, representing a state-of-the-art multifunctional electrocatalyst for alcohol oxidation reactions. In particular, the PtRhBiSnSb HEI achieves record-high methanol oxidation reaction (MOR) activity in an alkaline environment. Theoretical calculations demonstrate that the introduction of the fifth metal Rh enhances the electron-transfer efficiency in PtRhBiSnSb HEI nanoplates, which contributes to the improved oxidation capability. Meanwhile, robust electronic structures of the active sites are achieved due to the synergistic protections from Bi, Sn, and Sb sites. This work offers significant research advances in developing well-defined HEA with delicate control over compositions and properties.
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