Xing Tan, Zhenchen Tang, Huanhao Chen, Feng Zeng, Chalachew Mebrahtu
By substituting the anodic oxygen evolution reaction with the thermodynamically and kinetically more favorable ethanol oxidation reaction (EOR), energy consumption for hydrogen production can be significantly reduced while simultaneously generating value‐added chemicals. In this work, we developed a pulsed galvanostatic deposition strategy that mitigates the Au surface‐enrichment issue typically observed in conventional Pt–Au alloys. This method enables the direct co‐deposition of a Pt–Au alloy on nickel foam, structurally characterized by a Pt‐enriched surface and an Au‐rich bulk. This configuration proves highly advantageous for EOR: the Au‐rich bulk modulates the electronic structure and induces lattice distortion, while the Pt‐enriched surface provides abundant active sites for ethanol adsorption and oxidation. The synergy of these electronic and bifunctional effects enhances both intrinsic activity and accessible surface area, promoting ethanol oxidation to acetate via an acetaldehyde intermediate. The optimized Pt–Au/NF‐0.2 catalyst delivers an EOR current density of 331.2 mA cm −2 at 1.20 V versus RHE, surpassing monometallic Pt/NF and Au/NF. Furthermore, the system achieves an 82.8% Faradaic efficiency toward acetate and exhibits robust stability, retaining 92.9% of its activity after 300 CV cycles.