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Title: Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation

Photocatalysis has not found widespread industrial adoption, in spite of decades of active research, because the challenges associated with catalyst illumination and turnover outweigh the touted advantages of replacing heat with light. A demonstration that light can control product selectivity in complex chemical reactions could prove to be transformative. Here, we show how the recently demonstrated plasmonic behaviour of rhodium nanoparticles profoundly improves their already excellent catalytic properties by simultaneously reducing the activation energy and selectively producing a desired but kinetically unfavourable product for the important carbon dioxide hydrogenation reaction. Methane is almost exclusively produced when rhodium nanoparticles are mildly illuminated as hot electrons are injected into the anti-bonding orbital of a critical intermediate, while carbon monoxide and methane are equally produced without illumination. As a result, the reduced activation energy and super-linear dependence on light intensity cause the unheated photocatalytic methane production rate to exceed the thermocatalytic rate at 350°C.
Authors:
 [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [2] ;  [1]
  1. Duke Univ., Durham, NC (United States)
  2. Duke Univ., Durham, NC (United States); Army Aviation & Missile RD&E Center, Redstone Arsenal, AL (United States)
Publication Date:
Grant/Contract Number:
SC0012575
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; nanoparticles; photocatalysis
OSTI Identifier:
1367174

Zhang, Xiao, Li, Xueqian, Zhang, Du, Su, Neil Qiang, Yang, Weitao, Everitt, Henry O., and Liu, Jie. Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation. United States: N. p., Web. doi:10.1038/ncomms14542.
Zhang, Xiao, Li, Xueqian, Zhang, Du, Su, Neil Qiang, Yang, Weitao, Everitt, Henry O., & Liu, Jie. Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation. United States. doi:10.1038/ncomms14542.
Zhang, Xiao, Li, Xueqian, Zhang, Du, Su, Neil Qiang, Yang, Weitao, Everitt, Henry O., and Liu, Jie. 2017. "Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation". United States. doi:10.1038/ncomms14542. https://www.osti.gov/servlets/purl/1367174.
@article{osti_1367174,
title = {Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation},
author = {Zhang, Xiao and Li, Xueqian and Zhang, Du and Su, Neil Qiang and Yang, Weitao and Everitt, Henry O. and Liu, Jie},
abstractNote = {Photocatalysis has not found widespread industrial adoption, in spite of decades of active research, because the challenges associated with catalyst illumination and turnover outweigh the touted advantages of replacing heat with light. A demonstration that light can control product selectivity in complex chemical reactions could prove to be transformative. Here, we show how the recently demonstrated plasmonic behaviour of rhodium nanoparticles profoundly improves their already excellent catalytic properties by simultaneously reducing the activation energy and selectively producing a desired but kinetically unfavourable product for the important carbon dioxide hydrogenation reaction. Methane is almost exclusively produced when rhodium nanoparticles are mildly illuminated as hot electrons are injected into the anti-bonding orbital of a critical intermediate, while carbon monoxide and methane are equally produced without illumination. As a result, the reduced activation energy and super-linear dependence on light intensity cause the unheated photocatalytic methane production rate to exceed the thermocatalytic rate at 350°C.},
doi = {10.1038/ncomms14542},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}

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