Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy-猫眼课题宝

DOI：

10.1021/cbmi.4c00015

发表时间：

2024-03

期刊：

Chemical & Biomedical Imaging

影响因子：

--

通讯作者：

中科院分区：

其他

文献类型：

--

作者：

Dairong Liu;Linfei Li;Nan Jiang

金属负载的超薄氧化亚铁（FeO）由于其在多相催化中的广泛应用而引起了学术界和工业界的极大兴趣。然而，对FeO局部结构特征的化学洞察，尽管在阐明结构-性质关系方面至关重要，仍然难以捉摸。在这项工作中，我们报告了利用超高真空尖端增强拉曼光谱（UHV-TERS）和扫描隧道显微镜（STM）对金（Au）支持的超薄FeO进行纳米级化学探测。为了进行对比分析，使用单晶Au（111）和Au（100）衬底来调整FeO的界面性能。虽然STM图像显示Au（111）和Au（100）上的FeO纳米岛上的moirir超结构明显不同，但TERS通过类似的振动特征显示了FeO的相同化学性质。此外，结合TERS和STM测量，在Au（100）上发现了一个独特的褶皱FeO结构，这与FeO沉积导致Au（100）表面重构的重组有关。除了揭示Au衬底上超薄FeO的形态外，我们的研究还提供了对FeO在Au上的局部界面性质和相互作用的透彻理解，这可以为合理设计金属负载FeO催化剂提供启示。此外，这项工作还证明了结合TERS和STM在纳米尺度上化学探测金属支撑的超薄氧化物的结构特性方面具有很好的应用前景。

Metal-supported ultrathin ferrous oxide (FeO) has attracted immense interest in academia and industry due to its widespread applications in heterogeneous catalysis. However, chemical insight into the local structural characteristics of FeO, despite its critical importance in elucidating structure–property relationships, remains elusive. In this work, we report the nanoscale chemical probing of gold (Au)-supported ultrathin FeO via ultrahigh-vacuum tip-enhanced Raman spectroscopy (UHV-TERS) and scanning tunneling microscopy (STM). For comparative analysis, single-crystal Au(111) and Au(100) substrates are used to tune the interfacial properties of FeO. Although STM images show distinctly different moiré superstructures on FeO nanoislands on Au(111) and Au(100), TERS demonstrates the same chemical nature of FeO by comparable vibrational features. In addition, combined TERS and STM measurements identify a unique wrinkled FeO structure on Au(100), which is correlated to the reassembly of the intrinsic Au(100) surface reconstruction due to FeO deposition. Beyond revealing the morphologies of ultrathin FeO on Au substrates, our study provides a thorough understanding of the local interfacial properties and interactions of FeO on Au, which could shed light on the rational design of metal-supported FeO catalysts. Furthermore, this work demonstrates the promising utility of combined TERS and STM in chemically probing the structural properties of metal-supported ultrathin oxides on the nanoscale.