Efficient electrochemical hydrogen evolution reaction (HER) plays a key role in accelerating sustainable H2 production from water electrolysis, while its large-scale applications are hindered by the high cost of the state-of-the-art Pt catalyst. Herein, sub-monolayer Pt is controllably deposited on an intermetallic Pd3Pb nanoplate (AL-Pt/Pd3Pb) through a well-defined epitaxial growth. The atomic efficiency of active surface Pt layer is largely optimized and their electronic structure is simultaneously modulated by the Pd3Pb sub-strate, greatly enhancing the acidic HER. The AL-Pt/Pd3Pb exhibit an outstanding HER activity with only 13.8 mV overpotential to reach a current density of 10 mA/cm2 and a high mass activity 7834 A/gPd+Pt at - 0.05 V, both largely surpassing the commercial Pt/C (30 mV, 1486 A/gPt). In addition, the AL-Pt/Pd3Pb shows excellent stability and robustness in acidic HER condition during continuous 25 h chronoamperometry test. Density functional theory calcula-tions show that the improved intrinsic activity of AL-Pt/Pd3Pb is mainly derived from the charge transfer from Pd3Pb to sub-monolayer Pt, resulting in a strong electrostatic interaction that can stabilize the transition state of the rate-limiting Heyrovsky reaction and lower the barrier.

中文翻译：

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通过电荷转移促进氢析出反应在金属间 Pd3Pb 上的亚单层 Pt 的工程电子结构

高效的电化学析氢反应（HER）在加速水电解可持续制氢方面发挥着关键作用，而最先进的 Pt 催化剂的高成本阻碍了其大规模应用。在此，亚单层 Pt 通过明确的外延生长可控地沉积在金属间 Pd3Pb 纳米片（AL-Pt/Pd3Pb）上。活性表面 Pt 层的原子效率得到极大优化，同时它们的电子结构受到 Pd3Pb 衬底的调节，大大增强了酸性 HER。AL-Pt/Pd3Pb 表现出出色的 HER 活性，仅 13.8 mV 的过电位即可达到 10 mA/cm2 的电流密度和高质量活性 7834 A/gPd+Pt 在 - 0.05 V，两者都大大超过了商业 Pt/C (30 mV, 1486 A/gPt)。此外，在连续 25 小时计时电流法测试期间，AL-Pt/Pd3Pb 在酸性 HER 条件下显示出优异的稳定性和稳健性。密度泛函理论计算表明，AL-Pt/Pd3Pb 固有活性的提高主要来自于从 Pd3Pb 到亚单层 Pt 的电荷转移，产生了强静电相互作用，可以稳定限速层的过渡态。 Heyrovsky反应并降低了障碍。