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Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures

Nature Chemistry volume 3, pages 467472 (2011) | Download Citation

Abstract

Catalysis plays a critical role in chemical conversion, energy production and pollution mitigation. High activation barriers associated with rate-limiting elementary steps require most commercial heterogeneous catalytic reactions to be run at relatively high temperatures, which compromises energy efficiency and the long-term stability of the catalyst. Here we show that plasmonic nanostructures of silver can concurrently use low-intensity visible light (on the order of solar intensity) and thermal energy to drive catalytic oxidation reactions—such as ethylene epoxidation, CO oxidation, and NH3 oxidation—at lower temperatures than their conventional counterparts that use only thermal stimulus. Based on kinetic isotope experiments and density functional calculations, we postulate that excited plasmons on the silver surface act to populate O2 antibonding orbitals and so form a transient negative-ion state, which thereby facilitates the rate-limiting O2-dissociation reaction. The results could assist the design of catalytic processes that are more energy efficient and robust than current processes.

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Acknowledgements

We acknowledge support from the US Department of Energy Office of Basic Energy Sciences, Division of Chemical Sciences (FG-02-05ER15686) and the National Science Foundation (CTS-CAREER 0543067, NSF-0966700). 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 stimulating discussions and helpful insights.

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

    • Phillip Christopher
    • , Hongliang Xin
    •  & Suljo Linic

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Contributions

P.C., H.X. and S.L. devised and developed the project. P.C. carried out experimental work and analysis. H.X. performed the DFT calculations. All the authors wrote the manuscript. S.L. is the PhD adviser of H.X. and P.C.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Suljo Linic.

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https://doi.org/10.1038/nchem.1032

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