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. 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.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Xiao
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Xueqian
authors.identifier: 0000-0002-1197-3743
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Du
authors.initials: D
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Neil Qiang
authors.initials: NQ
authors.lastname: Su
authors.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Weitao
authors.initials: W
authors.lastname: Yang
authors.affiliation: Department of Physics, Duke University, Durham, North Carolina 27708, USA.|Army Aviation &Missile RD&E Center, Redstone Arsenal, Alabama 35898, USA.
authors.forename: Henry O
authors.identifier: 0000-0002-8141-3768
authors.initials: HO
authors.lastname: Everitt
authors.affiliation: Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Jie
authors.initials: J
authors.lastname: Liu