Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation.

Journal Article

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. 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.

Full Text

Duke Authors

Cited Authors

  • Zhang, X; Li, X; Zhang, D; Su, NQ; Yang, W; Everitt, HO; Liu, J

Published Date

  • February 23, 2017

Published In

Volume / Issue

  • 8 /

Start / End Page

  • 14542 -

PubMed ID

  • 28230100

Electronic International Standard Serial Number (EISSN)

  • 2041-1723

Digital Object Identifier (DOI)

  • 10.1038/ncomms14542

Language

  • eng