Site-selective CO disproportionation mediated by localized surface plasmon resonance excited by electron beam

Abstract

Recent reports of hot-electron-induced dissociation of small molecules, such as hydrogen, demonstrate the potential application of plasmonic nanostructures for harvesting light to initiate catalytic reactions. Theories have assumed that plasmonic catalysis is mediated by the energy transfer from nanoparticles to adsorbed molecules during the dephasing of localized surface plasmon (LSP) modes optically excited on plasmonic nanoparticles. However, LSP-induced chemical processes have not been resolved at a sub-nanoparticle scale to identify the active sites responsible for the energy transfer. Here, we exploit the LSP resonance excited by electron beam on gold nanoparticles to drive CO disproportionation at room temperature in an environmental scanning transmission electron microscope. Using in situ electron energy-loss spectroscopy with a combination of density functional theory and electromagnetic boundary element method calculations, we show at the subparticle level that the active sites on gold nanoparticles are where preferred gas adsorption sites and the locations of maximum LSP electric field amplitude (resonance antinodes) superimpose. Our findings provide insight into plasmonic catalysis and will be valuable in designing plasmonic antennas for low-temperature catalytic processes.

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Fig. 1: DFT-calculation-based choice of Au nanoprisms supported by TiO2 particles to realize a variety of local CO adsorption probabilities.
Fig. 2: Simulated electron-energy loss probability and induced electric field originating from electron-beam-excited LSP resonance on a Au nanoprism on TiO2 in a cantilevered configuration.
Fig. 3: EELS measurements of electron-beam-excited LSP resonance on a Au nanoprism on TiO2 in a cantilevered configuration.
Fig. 4: Effect of CO adsorption on LSP resonance energy.
Fig. 5: CO disproportionation reaction driven by electron-beam-excited LSP resonance.

Data availability

All relevant data are available from the corresponding author upon request.

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Acknowledgements

The authors thank R. Egerton (University of Alberta), P. Batson (Rutgers University), U. Hohenester (Karl-Franzens-Universität Graz), P. Longo (Gatan), Q. Qiao (Temple University), J. Kohoutek (NIST) and A. Herzing (NIST) for useful discussions. W.D.Y., P.A.L. and C.W. acknowledge support under the Cooperative Research Agreement between the University of Maryland and the National Institute of Standards and Technology Physical Measurement Laboratory, award 70NANB14H209, through the University of Maryland.

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W.D.Y., C.W., P.A.L., and R.S. conceived and designed the research. W.D.Y. and P.A.L. fabricated the gold antennas. W.D.Y. conducted in situ measurements in the ESTEM and processed the data. W.D.Y. and P.A.L. determined the crystallographic structure of the gold antennas. L.A.F. carried out DFT calculations. W.D.Y., L.S. and H.J.L. carried out electromagnetic BEM calculations. All authors contributed to writing the manuscript.

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Correspondence to Renu Sharma.

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Supplementary Figs. 1–12, Supplementary Tables 1,2, Supplementary refs. 1–15

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Yang, W.D., Wang, C., Fredin, L.A. et al. Site-selective CO disproportionation mediated by localized surface plasmon resonance excited by electron beam. Nat. Mater. 18, 614–619 (2019). https://doi.org/10.1038/s41563-019-0342-3

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