Issue 41, 2023

Ligand-mediated electron transport channels enhance photocatalytic activity of plasmonic nanoparticles

Abstract

Photoexcitation of noble metal nanoparticles creates surface plasmons which further decay to form energetic charge carriers. These charge carriers can initiate and/or accelerate various chemical processes at nanoparticle surfaces, although the efficiency of such processes remains low as a large fraction of these carriers recombine before they can reach the reaction sites. Thus efficient utilization of these charge carriers requires designing nanostructures that promote the separation of charges and their transport toward the reaction sites. Here we demonstrate that covalently bound surface-coating ligands with suitable orbital alignment can provide electron transport channels boosting hot electron extraction from a gold nanostructure leading to a huge enhancement in the rate of hydrogen evolution reaction (HER) under NIR excitation. A (p)Br-Ph-SH substituted gold nanoprism (AuTP) substrate produced ∼4500 fold more hydrogen compared to a pristine AuTP substrate under 808 nm excitation. Further experimental and theoretical studies on a series of substituted benzene-thiol bound AuTP substrates showed that the extent of the ligand-mediated HER enhancement depends not only on the polarity of the ligand but on the interfacial orbitals interactions.

Graphical abstract: Ligand-mediated electron transport channels enhance photocatalytic activity of plasmonic nanoparticles

Supplementary files

Article information

Article type
Communication
Submitted
14 Jun 2023
Accepted
30 Sep 2023
First published
09 Oct 2023

Nanoscale, 2023,15, 16552-16560

Ligand-mediated electron transport channels enhance photocatalytic activity of plasmonic nanoparticles

G. Joshi, R. Kashyap, K. Patrikar, A. Mondal and S. Khatua, Nanoscale, 2023, 15, 16552 DOI: 10.1039/D3NR02829A

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