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Title: Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation

Abstract

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:
Research Org.:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1367174
Grant/Contract Number:  
SC0012575
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; nanoparticles; photocatalysis

Citation Formats

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., 2017. 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. Thu . "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},
issn = {2041-1723},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}

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Cited by: 18 works
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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State
journal, March 2013


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Photodetection with Active Optical Antennas
journal, May 2011

  • Knight, M. W.; Sobhani, H.; Nordlander, P.
  • Science, Vol. 332, Issue 6030, p. 702-704
  • DOI: 10.1126/science.1203056