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Nano Research 2019, 12(8): 1906-1911 https://doi.org/10.1007/s12274-019-2457-x
Research Article | Issue | Published: 14 June 2019

Confirming nonthermal plasmonic effects enhance CO2 methanation on Rh/TiO2 catalysts

Show Author's Information Xueqian Li1,  Henry O. Everitt2,3( ),  Jie Liu1( )
Department of Chemistry,Duke University,Durham, NC,27708,USA;
Army Combat Capabilities Development Command,Aviation & Missile Center,Redstone Arsenal, AL,35898,USA;
Department of Physics,Duke University,Durham, NC,27708,USA;
Keywords:
carbon dioxide reduction, plasmonic photocatalysis, hot carriers, photothermal heating, rhodium nanoparticles
Topics:
Carbon dioxideCatalysis Catalyst selectivity HydrogenationPhotocatalystsPlasmonic nanoparticles Plasmonics Reaction ratesSurface propertiesTitanium compounds
Cite this article:
Li X, Everitt HO, Liu J. Confirming nonthermal plasmonic effects enhance CO2 methanation on Rh/TiO2 catalysts. Nano Research, 2019, 12(8): 1906-1911. https://doi.org/10.1007/s12274-019-2457-x
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Abstract Full text Electronic supplementary material About this article

In some cases, illumination of traditional thermal catalysts and tailored plasmonic photocatalysts may synergistically combine thermal and nonthermal mechanisms to enhance reaction rates and improve product selectivity at reduced temperatures. To understand how these attributes are achieved in plasmon-driven catalysis, these intertwined thermal and nonthermal effects must be untangled. Here, we show how a novel indirect illumination technique, in conjunction with precisely monitored thermal profiles of the catalyst, can confirm and clarify the role of nonthermal effects in plasmon-enhanced carbon dioxide methanation on a Rh/TiO2 photocatalyst. We find that the extracted nonthermal methane production rate has a linear dependence on the top surface temperature, distinctly different from an exponential dependence for thermal catalysis. We also find that the apparent quantum efficiency from the nonthermal contribution has no dependence on light intensity but maintains a linear dependence on top surface temperatures between 200 and 350 ℃. The clear exposition of nonthermal effects in the Rh/TiO2 plasmonic photocatalyst illustrates how this methodology may be applied for the quantitative evaluation of thermal and nonthermal light effects in other plasmon-enhanced catalytic reactions.


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About this article

Confirming nonthermal plasmonic effects enhance CO2 methanation on Rh/TiO2 catalysts

Show Author's information Xueqian Li1, Henry O. Everitt2,3( ), Jie Liu1( )
Department of Chemistry,Duke University,Durham, NC,27708,USA;
Army Combat Capabilities Development Command,Aviation & Missile Center,Redstone Arsenal, AL,35898,USA;
Department of Physics,Duke University,Durham, NC,27708,USA;

Abstract

In some cases, illumination of traditional thermal catalysts and tailored plasmonic photocatalysts may synergistically combine thermal and nonthermal mechanisms to enhance reaction rates and improve product selectivity at reduced temperatures. To understand how these attributes are achieved in plasmon-driven catalysis, these intertwined thermal and nonthermal effects must be untangled. Here, we show how a novel indirect illumination technique, in conjunction with precisely monitored thermal profiles of the catalyst, can confirm and clarify the role of nonthermal effects in plasmon-enhanced carbon dioxide methanation on a Rh/TiO2 photocatalyst. We find that the extracted nonthermal methane production rate has a linear dependence on the top surface temperature, distinctly different from an exponential dependence for thermal catalysis. We also find that the apparent quantum efficiency from the nonthermal contribution has no dependence on light intensity but maintains a linear dependence on top surface temperatures between 200 and 350 ℃. The clear exposition of nonthermal effects in the Rh/TiO2 plasmonic photocatalyst illustrates how this methodology may be applied for the quantitative evaluation of thermal and nonthermal light effects in other plasmon-enhanced catalytic reactions.

Keywords: carbon dioxide reduction, plasmonic photocatalysis, hot carriers, photothermal heating, rhodium nanoparticles

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Publication history
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Acknowledgements

Publication history

Received: 14 February 2019
Revised: 05 May 2019
Accepted: 05 June 2019
Published: 14 June 2019
Issue date: August 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

This research is supported by the National Science Foundation (CHE-1565657) and the Army Research Office (Award W911NF- 15-1-0320). X. L. is supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

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