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Controlling energy flow in multimetallic nanostructures for plasmonic catalysis

Abstract

It has been shown that photoexcitation of plasmonic metal nanoparticles (Ag, Au and Cu) can induce direct photochemical reactions. However, the widespread application of this technology in catalysis has been limited by the relatively poor chemical reactivity of noble metal surfaces. Despite efforts to combine plasmonic and catalytic metals, the physical mechanisms that govern energy transfer from plasmonic metals to catalytic metals remain unclear. Here we show that hybrid core–shell nanostructures in which a core plasmonic metal harvests visible-light photons can selectively channel that energy into catalytically active centres on the nanostructure shell. To accomplish this, we developed a synthetic protocol to deposit a few monolayers of Pt onto Ag nanocubes. This model system allows us to conclusively separate the optical and catalytic functions of the hybrid nanomaterial and determine that the flow of energy is strongly biased towards the excitation of energetic charge carriers in the Pt shell. We demonstrate the utility of these nanostructures for photocatalytic chemical reactions in the preferential oxidation of CO in excess H2. Our data demonstrate that the reaction occurs exclusively on the Pt surface.

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Figure 1: Characterization of Ag–Pt nanocubes.
Figure 2: Measured and calculated optical extinction, absorption, and scattering of Ag and Ag–Pt nanocubes.
Figure 3: Photocatalytic reactor studies.

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Acknowledgements

This work was primarily supported by the National Science Foundation (NSF) (CBET-1437601 and CBET- 1702471). The synthesis was developed with the support of the US Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences (FG-02-05ER15686). Secondary support for the development of analytical tools used to analyse the data was provided by NSF (CBET-1436056 and CHE- 1362120). The electron microscopy measurements were supported by the University of Michigan College of Engineering and by NSF (DMR-0723032). S.L. also acknowledges the partial support of the Technical University Munich – Institute for Advance Study.

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U.A. and S.L. developed the project. U.A. carried out the syntheses, characterization, optical measurements and reactor studies. S.C. performed all the optical simulations. All the authors wrote the manuscript and Supplementary Information.

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Correspondence to Suljo Linic.

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The authors declare no competing financial interests.

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Aslam, U., Chavez, S. & Linic, S. Controlling energy flow in multimetallic nanostructures for plasmonic catalysis. Nature Nanotech 12, 1000–1005 (2017). https://doi.org/10.1038/nnano.2017.131

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