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The extensive research on ultrathin ferrous oxide (FeO) islands and films over the last few decades has significantly contributed to the understanding of their structural and catalytic properties. In this regard, the local chemical properties of FeO edges, such as their metal affinity, play a critical role in determining and tuning the catalytic reactivity of FeO, which however remains largely unexplored. In this work, we use scanning tunneling microscopy (STM) to study the interaction of Pd and Pt with FeO grown on Au(111). Different Fe affinities for Pd and Pt are demonstrated by the preferential growth of Pd on the Fe-terminated edge and Pt on the O-terminated edge of FeO nanoislands, resulting in selectively blocked FeO edges. In addition to revealing the different metal affinities of FeO edges, our results provide new insights into the edge reactivity of FeO/Au(111) and suggest an approach for controlling the selectivity of FeO catalysts.
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Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy
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.
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- Award ID(s):
- 2211474
- PAR ID:
- 10501120
- Publisher / Repository:
- ACS Publishing
- Date Published:
- Journal Name:
- Chemical & Biomedical Imaging
- ISSN:
- 2832-3637
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/cbmi.4c00015
