4.8 Article

Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer

Journal

NANOSCALE
Volume 8, Issue 2, Pages 796-803

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c5nr04942c

Keywords

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Funding

  1. Swiss National Science Foundation [200020-126694]
  2. European Research Council under the European Union's Seventh Framework Program [247283]
  3. ETH research grant [2200, ETH-08 14-2]
  4. Swiss National Science Foundation Advanced Researcher fellowship [145392]

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Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol(-1) and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.

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