Zhou Jinyu, Zha Xiuling, Ma Siying, Wu Sihui, Ma Chunlan, Chen Gaoyuan, Chen Zhigang, Zhang Taoyang, Chen Zhiwei, Wang Di, Yan Yuxiang, Sun Yuqing, Ren Hengdong, Sun Hongzhao, Wu Xinglong, Zhao Zhigang, Cong Shan
National Laboratory of Solid States Microstructures and School of Physics, Nanjing University, Nanjing, 210093, Jiangsu, China.
Key Lab of Nanodevices and Applications, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China.
Nat Commun. 2025 Aug 28;16(1):8042. doi: 10.1038/s41467-025-63224-5.
Metal single atoms have been demonstrated to induce surface-enhanced Raman scattering (SERS) due to their effectiveness in the modification of electronic structure. However, precisely modulating the relative positions of metal single atoms on sub-nanolattices remains a formidable challenge, which makes SERS studies of metal single atoms dependent on localized environments still lacking. Herein, we rely on polyethylene glycol (PEG) as a soft template to achieve the modulation of the relative positions of W atoms on titanate nanotubes (W-TNTs) and probe the local-environment-dependent SERS induced by metal single atoms based on this technique. We find that the relative position of the W single atoms greatly affects their SERS performance. This phenomenon has been attributed to the difference in charge transfer ability between single W atoms of different configurations, with isolated W atoms inducing a significantly higher density of electronic states near the Fermi energy than associated W atoms, leading to an enhanced polarization of the probe molecule and subsequently a stronger Raman signal. Our findings demonstrate a technique to effectively control the relative positions of single atoms and provide insights into single-atom-induced SERS associated with localized environments, which will facilitate the rational design of SERS substrates based on metal single atoms.
由于金属单原子在电子结构修饰方面的有效性，已证明其能诱导表面增强拉曼散射（SERS）。然而，精确调节亚纳米晶格上金属单原子的相对位置仍然是一项艰巨的挑战，这使得对依赖局部环境的金属单原子的SERS研究仍然不足。在此，我们依靠聚乙二醇（PEG）作为软模板来实现钛酸盐纳米管（W-TNTs）上W原子相对位置的调节，并基于该技术探测由金属单原子诱导的依赖局部环境的SERS。我们发现W单原子的相对位置极大地影响其SERS性能。这种现象归因于不同构型的单个W原子之间电荷转移能力的差异，孤立的W原子在费米能级附近诱导的电子态密度明显高于缔合的W原子，导致探针分子的极化增强，进而产生更强的拉曼信号。我们的研究结果展示了一种有效控制单原子相对位置的技术，并为与局部环境相关的单原子诱导SERS提供了见解，这将有助于基于金属单原子的SERS基底的合理设计。
