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Engineering the surface electronic structure of Pd via Bi alloying and N-doped carbon support for enhanced ethanol oxidation
Journal article   Peer reviewed

Engineering the surface electronic structure of Pd via Bi alloying and N-doped carbon support for enhanced ethanol oxidation

Haofeng Lu, Junping Tang, Zhenghu Zhu, Xunwang Duan, Xinyu Li, Cheng Chen, Xinfeng Wu, Yonghou Xiao, Lexing You, Xinzhou Ma, …
Electrochimica acta, v 548, 147930
01 Feb 2026

Abstract

Bifunctional effect Ethanol oxidation Metal–support interaction MOF-derived carbon PdBi alloy
•PdBi alloy nanoparticles are anchored on ZIF-8-derived N-doped carbon.•Electronic modulation downshifts Pd d-band center, weakening CO adsorption.•Bi enables early OH⁻ adsorption for efficient oxidative removal of intermediates.•High ECSA and strong metal–support interaction enhance charge transfer.•Synergy of alloying and N-doped support boosts EOR activity and stability. Engineering the surface electronic structure of Pd-based catalysts is crucial for enhancing ethanol oxidation reaction (EOR) kinetics and durability in alkaline direct ethanol fuel cells. Herein, we report a high-performance PdBi alloy electrocatalyst supported on nitrogen-doped carbon monolith foam (CMF) derived from zeolitic imidazolate framework-8 (ZIF-8) pyrolysis and denoted as Pd₃Bi₁@CMF. The catalyst exhibits a mass activity of 1920 mA mg⁻¹Pd—2.8-fold higher than commercial Pd/C—attributed to its high electrochemical surface area (51.2 m² g⁻¹Pd) and uniform dispersion of ∼5.7 nm nanoparticles. X-ray photoelectron spectroscopy (XPS) confirms Bi-induced downshift of Pd 3d binding energy, weakening COads adsorption, while Bi promotes OH⁻ activation for oxidative removal of intermediates via a bifunctional mechanism. Strong metal–support interaction with N-doped CMF enhances structural stability, enabling 65.6 % activity retention after 300 CV cycles. Rotating disk electrode (RDE) analysis reveals a 5.2-electron transfer pathway, approaching the theoretical five-electron pathway for complete ethanol-to-acetate conversion. This study demonstrates that synergistic modulation of the surface electronic structure through alloying and rational support design offers a powerful strategy for developing advanced, durable, and highly active Pd-based EOR electrocatalysts. Facile Synthesis and Characterization of PdxBiy@CMFPdx​Biy​@CMF Composite Material Derived from ZIF-8 for Enhanced Catalytic Performance [Display omitted]

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Electrochemistry
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