Effect of Silica Supports on Plasmonic Heating of Molecular Adsorbates as Measured by Ultrafast Surface-Enhanced Raman Thermometry

Emily L. Keller, Hyunho Kang, Christy L Haynes, Renee R Frontiera

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Plasmonic materials show great potential for selective photocatalysis under relatively mild reaction conditions. However, the catalytic activity of these plasmonic catalysts can also depend upon the support material that stabilizes the catalysts, where the composition of the catalytic support may change the overall photocatalytic efficiency and yield. It is unknown how changes in the support material may change the plasmon-driven photocatalysis, which may be initiated by plasmon-derived hot carriers, localized heating, or enhanced electromagnetic fields. Herein, we probe the effects of catalytic supports on heating in plasmon-driven catalysis by examining various gold nanoparticle oxide systems. We use ultrafast surface-enhanced Raman thermometry to measure the effective temperature, equivalent to the vibrational kinetic energy, of reporter molecules located between plasmonic gold nanostructures and local environments ranging from ligands to mesoporous silica shells to silica shells. Upon photoexcitation, the transient effective temperature, equivalent to the energy deposited into a vibrational mode, of adsorbed molecules on the silica-coated samples increases, and the energy quickly dissipates within 3 ps. However, the baseline effective temperature that arises from the surface-enhanced Raman spectroscopy probing process depends upon the encapsulant, where the energy deposition differs by 200-300 K between the ligand-coated (citrate or CTAB) and the silica-coated samples. Adsorbates surrounded by a silica shell experience significantly higher effective temperatures than the adsorbates surrounded by ligands or solvent, likely because of the differing effective heat capacities of these media. Taken together, this work shows that a silica support impacts the localized heating of molecular adsorbates on the gold surface and may play a role in enhanced plasmonic photocatalysis because of increased thermal contributions.

Original languageEnglish (US)
Pages (from-to)40577-40584
Number of pages8
JournalACS Applied Materials and Interfaces
Volume10
Issue number47
DOIs
StatePublished - Nov 28 2018

Bibliographical note

Funding Information:
We thank Professor Xiaojia Wang (University of Minnesota) for helpful discussions. Contributions by E.L.K. and R.R.F. are based on the work supported by the Air Force Office of Scientific Research under AFOSR award no. FA9550-15-1-0022 and by the University of Minnesota Doctoral Dissertation Fellowship. Contributions by H.K. and C.L.H. were supported by the National Science Foundation under the Center for Sustainable Nanotechnology, CHE-1503408. The CSN is part of the Centers for Chemical Innovation Program. Parts of this work were carried out in the Characterization Facility at the University of Minnesota which receives partial support from the NSF through the MRSEC program (DMR-1420013).

Funding Information:
We thank Professor Xiaojia Wang (University of Minnesota) for helpful discussions. Contributions by E.L.K. and R.R.F. are based on the work supported by the Air Force Office of Scientific Research under AFOSR award no. FA9550-15-1-0022 and by the University of Minnesota Doctoral Dissertation Fellowship. Contributions by H.K. and C.L.H. were supported by the National Science Foundation under the Center for Sustainable Nanotechnology, CHE-1503408. The CSN is part of the Centers for Chemical Innovation Program. Parts of this work were carried out in the Characterization Facility at the University of Minnesota, which receives partial support from the NSF through the MRSEC program (DMR-1420013).

Keywords

  • plasmonic heating
  • plasmonic photocatalysis
  • ultrafast surface-enhanced Raman spectroscopy

How much support was provided by MRSEC?

  • Shared

Reporting period for MRSEC

  • Period 5

PubMed: MeSH publication types

  • Journal Article

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