Plasmon-Mediated Surface Functionalization: New Horizons for the Control of Surface Chemistry on the Nanoscale

Abstract

The combination of plasmonics and surface chemistry is a fastgrowing field of research, with promising prospects for a wide range of applications, including analytical chemistry, sensing, photocatalysis, photovoltaics and nanomedicine. It takes advantage of the confined electromagnetic fields, local heat generation and hot carrier excitation, that accompany plasmon resonances to incorporate molecular functionalities into engineered nanomaterials with a spatial control at the nanoscale. This review aims to provide a concise overview of the main plasmon-mediated surface functionalization strategies developed so far, and explains how it renews the toolbox of surface chemistry approaches. Plasmon-mediated surface functionalization appears to offer an unprecedented fast and cheap large scale "bottom-up" approach to trigger site-selective surface functionalization and place molecules/nanomaterials into highly reactive regions (reactive spots) or high electromagnetic field regions (hot spots).(e) (a)Finally, efforts are still required to further improve the analytical performance of these advanced nano-interfaces for (bio-)sensing applications and detection of trace amount of analytes.

Plasmonic Gold Nanoparticles (AuNPs): Properties, Synthesis and their Advanced Energy, Environmental and Biomedical Applications

“…[10] Moreover, AuNPs are also successfully employing in biomedical applications that include biological markers, DNA sensors, molecular recognition systems, drug delivery applications, and optical imaging. [11] The unique, advanced, and enhanced characteristics of plasmonic AuNPs are firmly based on the NPs stabilization, [12] surface functionality, [13,14] interparticle distance, [15] along with their size and morphology, which can be controlled by the help of synthesis. Therefore, the synthetic routes, reaction conditions, and precursors should be chosen according to the desired characteristics.…”

“…The unique, advanced, and enhanced characteristics of plasmonic AuNPs are firmly based on the NPs stabilization, [12] surface functionality, [13,14] interparticle distance, [15] along with their size and morphology, which can be controlled by the help of synthesis. Therefore, the synthetic routes, reaction conditions, and precursors should be chosen according to the desired characteristics [12] .…”

Confinement Effect of Plasmon for the Fabrication of Interconnected AuNPs through the Reduction of Diazonium Salts

“…Recently, many studies on the topic of plasmon-driven chemical reaction have been reviewed [ 40 , 41 , 42 ], including the reduction of nitro-aromatic compounds on supported AuNPs illuminated by a low-intensity UV light [ 43 ]. However, the plasmon-driven reduction reaction has shown a lower efficiency than those with additional photocatalysts inside.…”

Kinetics of Plasmon-Driven Hydrosilylation of Silicon Surfaces: Photogenerated Charges Drive Silicon- Carbon Bond Formation

“…[5][6][7][8][9] Localized surface plasmon resonance (LSPR) in metallic nanostructures is a well established as the platform for surface enhanced Raman spectroscopy (SERS), and has seen increasing interest as a driver of highly localized surface chemistry, as described beautifully in a recent review. 10 Depending on the size and other properties of the metallic nanostructures, illumination with the resonant optical wavelength to excite LSPR modes can be used to drive surface chemical reactions. Published examples include silicon-carbon bond formation on silicon surfaces via hydrosilylation of alkenes and alkynes, [11][12][13] aryl monolayer formation on gold through organic iodide cleavage, 14 thiol-ene Click chemistry on gold surfaces , 15 several examples of localized polymerization , [16][17][18][19][20][21] and spatially selective activation of light-sensitive monolayers in close proximity to gold colloids, 22 among others.…”

“…The mechanisms for the plasmon-driven surface chemistry appear to vary, and have been proposed to result from the strong and confined electromagnetic field, local generation of heat, or hot carriers, although it is very challenging to parse out the precise roles of the LSPR. 10 Previously, our group has demonstrated the use of 'plasmonic stamps' comprising arrays of either ordered and disordered gold nanoparticles integrated with flexible and optically transparent PDMS. [11][12][13] Upon illumination with visible light that corresponds with the maximum of the LSPR-based absorption of the gold nanoparticles, these stamps drive the patterned hydrosilylation of alkene and alkyne "inks" on Si-H-terminated surfaces in ~1 h at room temperature.…”