Improving the activity and stability of Pt-based electrocatalysts is still crucial for hydrogen generation applications. In this study, we investigated the catalytic properties of Cu-doped Pt alloy nanostructures synthesized by the modified polyol method, and compared the performance of PtCu catalyst with that of commercially available Pt/C for the hydrogen evolution reaction (HER) at room temperature. Structural analyses revealed that the PtCu catalysts exhibited fcc-$Fm\overline{3}m$ crystal structure with an average particle size below 5 nm. The HER performance of the catalysts showed overpotential of around −1.0 V (vs. Ag/AgCl) and Pt_0.25Cu_0.75 and Pt_0.75Cu_0.25 catalysts exhibited enhanced performance in 1 M KOH. The Pt_0.75Cu_0.25 catalyst exhibited distinct performance, with the highest mass activity found to be 62.80 mA mg⁻¹_Pt. The most active Pt_0.75Cu_0.25 catalysis for the HER process had the lowest onset potential of 0.989 V and Tafel slope of 35.5 mV dec⁻¹, which were an improvement compared to commercially available Pt/C catalysts. First principle DFT calculations confirmed the stabilities of Pt₁Cu₃, Pt₁Cu₁ and Pt₃Cu₁ compositions as ordered alloy structures. Nudged elastic band method calculations and the d-band model verified the higher catalytic activity of Pt–Cu nanoparticles compared to pure nanoparticles and point out the relevance of a synergistic effect of Pt and Cu atoms on water dissociation. According to DFT calculations, Cu and Pt sites significantly influenced the adsorption of H₂O and H, respectively, for splitting water molecules. While the Pt₅₉Cu₂₀ cluster has the highest H₂O adsorption energy at the (100) atop site of Cu atoms, H adsorption occurs at the (111) site of Pt atoms.

提高铂基电催化剂的活性和稳定性对于制氢应用仍然至关重要。在本研究中，我们研究了采用改良多元醇法合成的Cu掺杂Pt合金纳米结构的催化性能，并将PtCu催化剂与市售Pt/C催化剂在室温析氢反应（HER）中的性能进行了比较。结构分析表明 PtCu 催化剂表现出 fcc-$F米\stackrel{￣}{3}米$平均粒径小于5纳米的晶体结构。催化剂的 HER 性能显示出约 -1.0 V（相对于 Ag/AgCl）的过电势，并且 Pt _0.25 Cu _0.75和 Pt _0.75 Cu _0.25催化剂在 1 M KOH 中表现出增强的性能。Pt _0.75 Cu _0.25催化剂表现出独特的性能，最高质量活性为62.80 mA mg ^-1 _Pt。HER 过程中最活跃的 Pt _0.75 Cu _{0.25催化具有最低的起始电位 0.989 V 和塔菲尔斜率 35.5 mV dec} ^-1，与市售 Pt/C 催化剂相比，这是一项改进。_{第一原理DFT计算证实了Pt 1} Cu ₃、Pt ₁ Cu ₁和Pt ₃ Cu ₁组合物作为有序合金结构的稳定性。微移弹性带法计算和 d 带模型验证了 Pt-Cu纳米颗粒与纯纳米颗粒相比具有更高的催化活性，并指出了Pt 和 Cu 原子对水解离的协同效应的相关性。根据DFT计算，Cu和Pt位点显着影响H _2的吸附O和H分别用于分裂水分子。Pt ₅₉ Cu _20簇在Cu原子的(100)位点处具有最高的H _{2 O吸附能，而H吸附发生在Pt原子的(111)位点处。}