@article{10902/35002,
year = {2018},
month = {3},
url = {https://hdl.handle.net/10902/35002},
abstract = {In plasmon-enhanced heterogeneous catalysis, illumination accelerates reaction rates by generating hot carriers and hot surfaces in the constituent nanostructured metals. In order to understand how photogenerated carriers enhance the nonthermal reaction rate, the effects of photothermal heating and thermal gradients in the catalyst bed must be confidently and quantitatively characterized. This is a challenging task considering the conflating effects of light absorption, heat transport, and reaction energetics. Here, we
introduce a methodology to distinguish the thermal and nonthermal contributions from plasmon-enhanced catalysts, demonstrated by illuminated rhodium nanoparticles on oxide
supports to catalyze the CO₂ methanation reaction. By simultaneously measuring the total reaction rate and the temperature gradient of the catalyst bed, the effective thermal reaction rate may be extracted. The residual nonthermal rate of the plasmonenhanced reaction is found to grow with a superlinear dependence on illumination intensity, and its apparent quantum efficiency reaches ∼46% on a Rh/TiO₂ catalyst at a surface temperature of 350 °C. Heat and light are shown to work synergistically in these reactions: the higher the temperature, the higher the overall nonthermal efficiency in plasmon-enhanced catalysis.},
organization = {This research is supported by the National Science Foundation (CHE-1565657) and the Army Research Office (Award W911NF-15-1-0320). X.Z. is supported by the Katherine Goodman Stern fellowship from the Graduate School, Duke University. X.L. is supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program. D.Z., N.Q.S., and W.Y. are supported by the Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012575. Y.G. and F.M. are supported by MICINN (Spanish Ministry of Science and Innovation, project
FIS2013-45854-P) and the Army Research Laboratory under Cooperative Agreement no. W911NF-17-2-0023. Y.G. thanks the University of Cantabria for the FPU grant.},
publisher = {American Chemical Society},
publisher = {Nano Lett. 2018, 18(3), 1714-1723},
title = {Plasmon-enhanced catalysis: distinguishing thermal and nonthermal effects},
author = {Zhang, Xiao and Li, Xueqian and Reish, Matthew E. and Zhang, Du and Su, Neil Qiang and Gutiérrez Vela, Yael and Moreno Gracia, Fernando and Yang, Weitao and Everitt, Henry O. and Liu, Jie},
}