4.8 Article

Metal-Polymer Heterojunction in Colloidal-Phase Plasmonic Catalysis

Journal

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 13, Issue 10, Pages 2264-2272

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.1c04242

Keywords

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Funding

  1. MCIN/AEI [PID2019-111772RB-I00]
  2. Basque Government [IT 1254-19]
  3. European Commission (EUSMI) [731019]
  4. European Research Council [ERC-CoG-2019 815128]

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This work presents the use of a water-soluble conjugated polymer as a surface ligand for gold nanoparticles to achieve plasmonic catalysis under visible light. The metal-polymer heterojunction, rich in sulfonate functional groups, contributes to the interaction between electron-donor molecules and the plasmonic photocatalyst. The tight binding of the polymer to the gold surface eliminates the need for conventional transition-metal surface cocatalysts and enhances the reactivity.
Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD+ to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal-polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD(+) reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity.

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