Molecular-Scale Insights into the Heterogeneous Interactions Between an m-Terphenyl Isocyanide Ligand and Noble Metal Nanoparticles

ORAL

Abstract

The structural and chemical properties of metal nanoparticles are often dictated by their interactions with molecular ligand shells. These interactions are highly material-specific and can vary significantly even among elements within the same group or materials with similar crystal structure. Precise characterization of ligand-metal interactions is crucial for the rational design of ligands and the functionalization of nanoparticles. In this study, we found that the ligation behavior with an m-terphenyl isocyanide molecule differs significantly between Au and Ag nanoparticles, with distinct ligand extraction efficiencies and size dependencies. Surface-enhanced Raman spectroscopy measurements revealed unique enhancement factors for two molecular vibrational modes between two metal surfaces, indicating different ligand binding geometries. Molecular-level characterization using scanning tunneling microscopy allowed us to directly visualize these variations between Ag and Au surfaces, which we assign as two distinct binding mechanisms. This molecular-scale visualization provides clear insights into the different ligand-metal interactions, as well as the chemical behavior and spectroscopic characteristics of isocyanide-functionalized nanoparticles.

*The authors acknowledge the use of facilities and instrumentation supported by National Science Foundation (NSF) through the UC San Diego Materials Research Science and Engineering Center (UCSD MRSEC) with Grant No. DMR-2011924. This work was primarily supported by the NSF under Grant CHE-2303936 (to Shaowei Li) and DMR-2011924 (UCSD MRSEC). This work also used the Expanse supercomputer at the San Diego Supercomputing Center through allocation CSD799 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by NSF grants No. 2138259, No. 2138286, No. 2138307, No. 2137603, and No. 2138296.

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Publication: https://arxiv.org/abs/2408.16192

Presenters

  • Liya Bi

    • University of California, San Diego

Authors

  • Liya Bi

    • University of California, San Diego

  • Yufei Wang

    • University of California, San Diego

  • Zhe Wang

    • University of California, Irvine

  • Alexandria Do

    • University of California, San Diego

  • Alexander Fuqua

    • University of California, San Diego

  • Krista P Balto

    • University of California, San Diego

  • Yanning Zhang

    • University of Electronic Science and Technology of China

  • Joshua S Figueroa

    • University of California, San Diego

  • Tod A Pascal

    • University of California, San Diego

  • Andrea R Tao

    • University of California, San Diego

  • Shaowei Li

    • University of California, San Diego