Plasmon-driven reaction controlled by the number of graphene layers and localized surface plasmon distribution during optical excitation

Abstract

Graphene-plasmonic hybrid platforms have attracted an enormous amount of interest in surface-enhanced Raman scattering (SERS); however, the mechanism of employing graphene is still ambiguous, so clarification about the complex interaction among molecules, graphene, and plasmon processes is urgently needed. We report that the number of graphene layers controlled the plasmon-driven, surface-catalyzed reaction that converts para-aminothiophenol (PATP)-to-p,p9-dimercaptoazobenzene (DMAB) on chemically inert, graphene-coated, silver bowtie nanoantenna arrays. The catalytic reaction was monitored by SERS, which revealed that the catalytic reaction occurred on the chemical inertness monolayer graphene (1G)-coated silver nanostructures. The introduction of 1G enhances the plasmon-driven surface-catalyzed reaction of the conversion of PATP-to-p,p9-DMAB. The chemical reaction is suppressed by bilayer graphene. In the process of the catalytic reaction, the electron transfer from the PATP molecule to 1G-coated silver nanostructures. Subsequently, the transferred electrons on the graphene recombine with the hot-hole produced by the localized surface plasmon resonance of silver nanostructures. Then, a couple of PATP molecules lost electrons are catalyzed into the p,p9-DMAB molecule on the graphene surface. The experimental results were further supported by the finite-difference time-domain method and quantum chemical calculations.

Hot‐Electron‐Mediated Photochemical Reactions: Principles, Recent Advances, and Challenges

“…Since 2010, various experimental and theoretical results have supported the production of DMAB from pATP by plasmon-driven surface-catalyzed chemical reactions. [61][62][63][64][65][66][67][68][69][70][71][72] Adv. Optical Mater.…”

“…[66] Recently, graphene-plasmonic nanostructure (Ag nanowire and bowtie nanoantenna arrays) hybrid platforms have been utilized for surface catalytic reactions. [67,68,88] Owing to the strong plasmon-exciton coupling, the Ag/graphene hybrid platform increased the plasmon-toelectron conversion efficiency and induced a significant accumulation of high-density hot electrons, thereby enhancing the efficiency of surface catalytic reactions in comparison with those individually assisted by single Ag nanowires or graphene monolayers. [67] Furthermore, the plasmon-driven surface-catalyzed reaction could be controlled by altering the electron transfer as a function of the number of graphene layers.…”

“…[67] Furthermore, the plasmon-driven surface-catalyzed reaction could be controlled by altering the electron transfer as a function of the number of graphene layers. [68] As mentioned above, DMAB can be produced from pNTP through plasmon-driven surface-catalyzed chemical reactions. In this photochemical reaction, four hot electrons are directly injected from plasmonic nanostructures into the nearby two pNTP molecules, participating in the conversion of pNTP to DMAB (Figure 10a).…”

A Numerical-Experimental Method for Drop Impact Analysis of Composite Landing Gear

“…Composite materials are widely used in aerospace, aircraft, marine, civil, automotive, sport [5], and even optical engineering [6][7][8][9][10]. This is due to their outstanding physical, mechanical, and thermal properties, particularly their high stiffness and strength to weight ratios, good fatigue strength, excellent corrosion resistance, and dimensional stability.…”

Plasmonic metal decorated titanium dioxide thin films for enhanced photodegradation of organic contaminants

“…In another study, the transformation of para-aminothiophenol to p,p'-dimercaptoazobenzene occurred on grapheme due to Ag nanoparticles and the chemical reaction was controlled by the localised surface plasmon [18].…”