Based on plasmonic metallic nanomaterials (NMs) with unique local surface plasmon resonance (LSPR), the photo-excited hot carrier-driven hydrogenation reaction becomes a new family of photocatalytic transformations in recent years. However, the high work function and rapid hot-carrier recombination of plasmonic NMs create huge barriers for widespread practical application. Herein, we propose a fascinating reactor of up-regulated electrochemical LSPR (EC-LSPR) driven hydrogenation reaction via the construction of hierarchical Au pine needles (H-Au PNs) with enhanced lightning rod effect under appropriate extra electric field. The plentiful elongated Au branches with sharp corners and edges can be served as excellent electron-transport channels for facilitating photo-excited hot carrier transmission and accelerating hot electron collection at nano-tips after plasmon decay. Additionally, the extra electric field with the applied voltage of − 0.8 V further improves the surface charge density and the internal polarization of H-Au PNs, boosting the separation efficiency of hot carriers as well as reducing the photoelectrochemical (PEC) potential on H-Au PNs. It directly leads to an effective activation enthalpy reduction to reach above the energy threshold of water splitting, which can achieve the direct plasmon-driven PEC-hydrogenation conversion of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) in aqueous solution, and the conversion rate constant is about 5 times higher than bare EC-driven conversion. The present work provides a new opportunity for the emerging direct plasmon-driven hydrogenation reaction.

基于具有独特局部表面等离子体共振（LSPR）的等离子体金属纳米材料（NMs），光激发热载流子驱动的氢化反应成为近年来新的光催化转化家族。然而，等离子体NMs的高功函数和快速的热载流子复合为广泛的实际应用创造了巨大的障碍。在此，我们提出了一种引人入胜的上调电化学 LSPR (EC-LSPR) 驱动的加氢反应反应器，通过在适当的额外电场下构建具有增强避雷针效应的分层金松针 (H-Au PNs)。大量具有尖角和边缘的细长 Au 分支可作为极好的电子传输通道，用于促进光激发热载流子传输并加速等离子体衰变后纳米尖端的热电子收集。此外，施加 - 0.8 V 电压的额外电场进一步提高了 H-Au PNs 的表面电荷密度和内部极化，提高了热载流子的分离效率并降低了 H-的光电化学（PEC）电位Au PN。它直接导致有效的活化焓降低达到水分解的能量阈值以上，从而可以实现 4-硝基苯硫酚 (4-NTP) 到 4-氨基苯硫酚 (4-ATP) 的直接等离子体驱动的 PEC 加氢转化。水溶液，并且转换率常数比裸EC驱动的转换高约5倍。目前的工作为新兴的直接等离子体驱动的氢化反应提供了新的机会。