Tunable Plasmonic Nanoparticles with Catalytically Active High-Index Facets

Abstract

Noble metal nanoparticles have been of tremendous interest due to their intriguing size- and shape-dependent plasmonic and catalytic properties. Combining tunable plasmon resonances with superior catalytic activities on the same metallic nanoparticle, however, has long been challenging because nanoplasmonics and nanocatalysis typically require nanoparticles in two drastically different size regimes. Here, we demonstrate that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, we have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high-index facets abundant on the particle surfaces. The nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time-resolved plasmon-enhanced spectroscopic measurements.

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions

“…A further synthesis challenge is successfully combining non-plasmonic metals without quenching the SPR of the plasmonic component as maintaining a large plasmonic cross section is critical for efficient light harvesting. The ability to independently tailor size, shape and optical properties of NPs present many opportunities for a multidimensional approach to integrate several features into catalyst design, as illustrated by Jing et al [24] Their tuneable plasmonic Ag@Au core shell nanodumbells for 4-nitrothiophenol reduction exhibited the optimal structure for enhanced catalytic activity through both the SPR and high index surface facets, coupled with highly sensitive time-resolved SERS monitoring of the reaction. Thus there will be considerable overlap between engineering NPs for probing reactions to gain fundamental insights into the mechanisms operating in plasmon mediated photocatalysis and also developing integrated SERS and catalysis active NPs for operando monitoring.…”

Analytical Modeling of the Light-to-Heat Conversion by Nanoparticle Ensemble under Radiation Action

“…Fig. 3 presents the temporal dependences of NP temperature T 0 and parameters P 2 , P 3 on t for different NP radii r 0 = 5, 25, 100 nm, I n = I 0 K abs = 1x10 2 , 1.6x10 2 , 1.65x10 3 W/cm 2 , t P ≈1x10 -9 s determined on the base of the analytical dependences (15,18,21). Immediately after commencement of irradiation the NP heating and its heat exchange with the surrounding medium (water) start.…”

“…INTRODUCTION In recent years the absorption of radiation energy by NPs, light-to-heat conversion, heat dissipation and exchange with a surrounding material (medium), and following thermal and accompanied phenomena have become increasingly important topics in nanotechnology . Many reasons exist for this interest, including the applications of the light-to-heat conversion in nanoenergy [1][2][3][4][5][6][7][8][9][10][11][12], in photothermal laser nanomedicine [13][14][15][16] and catalysis [17,18], in laser processing of NPs (laser induced transformation of NP size, shape and structure) [19][20][21][22][23][24], etc. These advances in nanotechnology are based on the efficiency of light-to-heat conversion, thermal effects and the processes induced by the laser-NP interaction [1][2][3][4][5][6][7][8][9][10][11][12].…”

Synthesis of gold/rare-earth-vanadate core/shell nanorods for integrating plasmon resonance and fluorescence

“…sensors [2], catalysis [3,4], photovoltaics [5,6], etc. Recently, great efforts in this area have been dedicated to create core/shell heterostructures using Au nanocrystals as seeds and growing different materials on their surface [7][8][9][10].…”