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Near-field and photocatalytic properties of mono- and bimetallic nanostructures monitored by nanocavity surface-enhanced Raman scattering

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Abstract

Localized surface plasmon resonances (LSPR) generated in a particle-film nanocavity enhance electric fields within a nanoscale volume. LSPR can also decay into hot carriers, highly energetic species that catalyze photocatalytic reactions in molecular analytes located in close proximity to metal surfaces. In this study, we examined the intensity of the electric field (near-field) and photocatalytic properties of plasmonic nanocavities formed by single nanoparticles (SNP) on single nanoplates (SNL). Using 4-nitrobenzenethiol (4-NBT) as a molecular reporter, we determined the near-field responses, as well as measured rates of 4-NBT dimerization into 4,4-dimercaptoazobenzene (DMAB) in the gold (Au) SNP on AuSNL nanocavity (Au-Au), as well as in AuSNP on AgSNL (Au-Ag), AgSNP on AuSNL (Ag-Au), and AgSNP on AgSNL (Ag-Ag) nanocavities using 532, 660, and 785 nm excitations. We observed the strongest near-field signals of 4-NBT at 660 nm in all examined plasmonic systems that is found to be substantially red-shifted relative to the LSPR of the corresponding nanoparticles. We also found that rates of DMAB formation were significantly greater in heterometal nanocavities (Au-Ag and Ag-Au) compared to their monometallic counterparts (Au-Au and Ag-Ag). These results point to drastic differences in plasmonic and photocatalytic properties of mono and bimetallic nanostructures.

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Acknowledgements

We are grateful to AgriLife Research of Texas A&M for the provided financial support. We also acknowledge Governor’s University Research Initiative (GURI) grant program of Texas A&M University, GURI Grant Agreement No. 12-2016, M1700437. R. W. acknowledges the financial support from the State Key Laboratory of Analytical Chemistry for Life Science, Nan**g University (No. SKLACLS2215).

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  1. Rui Wang and Zhe He contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nan**g, 210096, China

    Rui Wang

  2. Department of Biochemistry and Biophysics, Texas A&M University, College Station, TX, 77843, USA

    Rui Wang & Dmitry Kurouski

  3. Department of Biomedical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA

    Zhe He

  4. The Institute for Quantum Science and Engineering, Texas A&M University, College Station, TX, 77843, USA

    Zhe He & Dmitry Kurouski

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  1. Rui Wang
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Correspondence to Dmitry Kurouski.

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Near-field and photocatalytic properties of mono- and bimetallic nanostructures monitored by nanocavity surface-enhanced Raman scattering

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Wang, R., He, Z. & Kurouski, D. Near-field and photocatalytic properties of mono- and bimetallic nanostructures monitored by nanocavity surface-enhanced Raman scattering. Nano Res. 16, 1545–1551 (2023). https://doi.org/10.1007/s12274-022-4736-1

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