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Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures

Nature Materials volume 11, pages 1044–1050 (2012)Cite this article

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Abstract

The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝intensityn, with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

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Figure 1: Geometric and optical characteristics of plasmonic photocatalyst.
Figure 2: Reaction rate, quantum efficiency and KIE as a function of intensity and temperature.
Figure 3: Molecular model for electron-driven reactions on metals.
Figure 4: Unique features of plasmonic photocatalysts.

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Acknowledgements

We gratefully acknowledge support from United States Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences (FG-02-05ER15686) and the National Science Foundation (CBET-0966700, CBET-1132777 and CHE-1111770). S.L. acknowledges the DuPont Young Professor grant and the Camille Dreyfus Teacher-Scholar Award from the Camille Henry Dreyfus Foundation. We also acknowledge David B. Ingram for assistance with FDTD simulations.

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Authors and Affiliations

  1. Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA

    Phillip Christopher, Hongliang Xin, Andiappan Marimuthu & Suljo Linic

  2. Department of Chemical and Environmental Engineering, University of California, Riverside Riverside, California 92521, USA

    Phillip Christopher

  3. Program in Materials Science and Engineering, University of California, California 92521, Riverside Riverside, USA

    Phillip Christopher

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P.C., H.X., and S.L. developed the project and analysed the results. P.C. carried out experimental work. H.X. performed the DFT simulations. A.M. assisted with analysis. S.L. is the PhD adviser of P.C., H.X. and A.M.

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Correspondence to Suljo Linic.

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Christopher, P., Xin, H., Marimuthu, A. et al. Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures. Nature Mater 11, 1044–1050 (2012). https://doi.org/10.1038/nmat3454

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