Xiao Tiantian, Diao Peng
School of Materials Science and Engineering, Beihang University, Beijing, 100191, P. R. China.
Adv Mater. 2025 Jul;37(28):e2501069. doi: 10.1002/adma.202501069. Epub 2025 Apr 17.
The localized surface plasmon resonance (LSPR) of metal nanoparticles can substantially enhance the activity of photoelectrocatalytic (PEC) reactions. However, quantifying the respective contributions of different LSPR mechanisms to the enhancement of PEC performance remains an urgent challenge. In this work, Cu@CuO composites prepared by annealing CuO under an inert atmosphere and electrodeposited metal@CuO composites (M@CuO, M = Cu, Au, Ag, Pd, Pt) are employed as platform materials to investigate the LSPR effect on the PEC hydrogen evolution reaction (HER). All the composites exhibited remarkably LSPR-enhanced activity toward PEC HER. The contributions of two LSPR mechanisms, plasmon induced resonance energy transfer (PIRET) and hot electron transfer (HET), to the photocurrent on Cu@CuO and Cu@CuO are quantified by using different bands of incident light. Moreover, using M@CuO composites, the effects of both the metal species and the applied potential on HET are quantitatively investigated. The results reveal that a pronounced HET enhancement occurs only when the LSPR peak energy is lower than the semiconductor bandgap energy (E) and that HET strengthens as the applied potential becomes more negative for PEC HER. This work therefore provides a quantitative understanding of the roles of PIRET and HET in boosting PEC activity.
金属纳米粒子的局域表面等离子体共振（LSPR）能够显著增强光电催化（PEC）反应的活性。然而，量化不同LSPR机制对PEC性能增强的各自贡献仍然是一项紧迫的挑战。在这项工作中，通过在惰性气氛下对CuO进行退火制备的Cu@CuO复合材料以及电沉积的金属@CuO复合材料（M@CuO，M = Cu、Au、Ag、Pd、Pt）被用作平台材料，以研究LSPR对PEC析氢反应（HER）的影响。所有复合材料均表现出对PEC HER显著的LSPR增强活性。通过使用不同波段的入射光，量化了等离子体诱导共振能量转移（PIRET）和热电子转移（HET）这两种LSPR机制对Cu@CuO和Cu@CuO光电流的贡献。此外，使用M@CuO复合材料，定量研究了金属种类和施加电势对HET的影响。结果表明，仅当LSPR峰值能量低于半导体带隙能量（E）时，才会出现明显的HET增强，并且对于PEC HER，随着施加电势变得更负，HET会增强。因此，这项工作提供了对PIRET和HET在提高PEC活性中作用的定量理解。
