Search query: Surface-Plasmon-Driven Hot Electron Photochemistry

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abstract: Visible light driven photochemistry has continued to attract heightened interest due to its capacity to efficiently harvest solar energy and its potential to solve the global energy crisis. Plasmonic nanostructures boast broadly tunable optical properties coupled with catalytically active surfaces that offer a unique opportunity for solar photochemistry. Resonant optical excitation of surface plasmons produces energetic hot electrons that can be collected to facilitate chemical reactions. This review sums up recent theoretical and experimental approaches for understanding the underlying photophysical processes in hot electron generation and discusses various electron transfer models on both plasmonic metal nanostructures and plasmonic metal/semiconductor heterostructures. Following that are highlights of recent examples of plasmon driven hot electron photochemical reactions within the context of both cases. The review concludes with a discussion about the remaining challenges in the field and future opportunities for addressing the low reaction efficiencies in hot electron induced photochemistry.
author_names: Yuchao Zhang

Shuai He

Wenxiao Guo

Yue Hu

Jiawei Huang

Justin R Mulcahy

Wei David Wei
title: Surface Plasmon Driven Hot Electron Photochemistry.
venue: Chemical reviews
year: 2018

abstract: Photochemistry that can be driven at low incident photon flux on optically excited plasmonic nanoparticles is attracting increasing research interest because of the fundamental need to combine surface reaction and in situ spectroscopy as well as the opportunity that plasmon driven reactions may offer a pathway for efficient conversion of solar energy into fuel. In mechanistic studies of plasmon driven reactions to date, a great deal of emphasis is given to hot electron transfer. The results summarized in this Feature Article indicate that photochemistry on plasmonic nanoparticles can be induced by hot electron transfer from the nanoparticle to an unoccupied orbital of the adsorbate and/or by plasmon pumped electron transition from an occupied molecular orbital to an unoccupied molecular orbital of the adsorbate. The branching photochemical reaction of para aminothiophenol on the plasmonic gold surface depending on the presence of a cetyltrimethylammonium bromide surface ligand that influences the hot elec.
author_names: Tefera Entele Tesema

Bijesh Kafle

Terefe G Habteyes
title: Plasmon Driven Reaction Mechanisms: Hot Electron Transfer versus Plasmon Pumped Adsorbate Excitation
venue: The Journal of Physical Chemistry C
year: 2019

abstract: Hot electrons generated through plasmonic excitations in metal nanostructures show great promise for efficiently driving chemical reactions with light. However, the lifetime, yield, and mechanism of action of plasmon generated hot electrons involved in a given photocatalytic process are not well understood. Here, we develop ultrafast surface enhanced Raman scattering (SERS) as a direct probe of plasmon molecule interactions in the plasmon catalyzed dimerization of 4 nitrobenzenethiol to p,p' dimercaptoazobenzene. Ultrafast SERS probing of these molecular reporters in plasmonic hot spots reveals transient Fano resonances, which we attribute to near field coupling of Stokes shifted photons to hot electron driven metal photoluminescence. Surprisingly, we find that hot spots that yield more photoluminescence are much more likely to drive the reaction, which indirectly proves that plasmon generated hot electrons induce the photochemistry. These ultrafast SERS results provide insight into the relative reactivity of different plasmonic hot spot environments and quantify the ultrafast lifetime of hot electrons involved in plasmon driven chemistry.
author_names: Nathaniel C Brandt

Emily L Keller

Renee R Frontiera
title: Ultrafast Surface Enhanced Raman Probing of the Role of Hot Electrons in Plasmon Driven Chemistry.
venue: The journal of physical chemistry letters
year: 2016

abstract: Direct measurement of hot electron flux from a plasmonic Schottky nanodiode is important for obtaining fundamental insights explaining the mechanism for electronic excitation on a surface. Here, we report the measurement of photoinduced hot electrons on a triangular Au nanoprism on TiO2 under incident light with photoconductive atomic force microscopy (pc AFM) which is direct proof of the intrinsic relation between hot electrons and localized surface plasmon resonance. We find that the local photocurrent measured on the boundary of the Au nanoprism is higher than that inside the Au nanoprism, indicating that field confinement at the boundary of the Au nanoprism acts as a hot spot, leading to the enhancement of hot electron flow at the boundary. Under incident illumination with a wavelength near the absorption peak (645 nm) of a single Au nanoprism, localized surface plasmon resonance resulted in the generation of a higher photoinduced hot electron flow for the Au nanoprism/TiO2, compared with that at a wavelength of 532 nm. We show that the application of a reverse bias results in a higher photocurrent for the Au nanoprism/TiO2, which is associated with a lowering of the Schottky barrier height caused by the image force. These nanoscale measurements of hot electron flux with pc AFM indicate efficient photon energy transfer mediated by surface plasmons in hot electron based energy conversion.
author_names: Hyunhwa Lee

Hyunsoo Lee

Jeong Y Park
title: Direct Imaging of Surface Plasmon Driven Hot Electron Flux on the Au Nanoprism/TiO2.
venue: Nano letters
year: 2019

abstract: A continuous flow of hot electrons that are not at thermal equilibrium with the surrounding metal atoms is generated by the absorption of photons. Here we show that hot electron flow generated on a gold thin film by photon absorption (or internal photoemission) is amplified by localized surface plasmon resonance. This was achieved by direct measurement of photocurrent on a chemically modified gold thin film of metal semiconductor (TiO(2) Schottky diodes. The short circuit photocurrent obtained with low energy photons is consistent with Fowler's law, confirming the presence of hot electron flows. The morphology of the metal thin film was modified to a connected gold island structure after heating such that it exhibits surface plasmon. Photocurrent and optical measurements on the connected island structures revealed the presence of a localized surface plasmon at 550 20 nm. The results indicate an intrinsic correlation between the hot electron flow generated by internal photoemission and localized surface plasmon resonance.
author_names: Young Keun Lee

Chan Ho Jung

Jonghyurk Park

Hyungtak Seo

Gabor A Somorjai

Jeong Y Park
title: Surface plasmon driven hot electron flow probed with metal semiconductor nanodiodes.
venue: Nano letters
year: 2011

abstract: A pulse of high kinetic energy electrons (1 3 eV) in metals can be generated after surface exposure to external energy, such as the absorption of light or exothermic chemical processes. These energetic electrons are not at thermal equilibrium with the metal atoms and are called "hot electrons" The detection of hot electrons and understanding the correlation between hot electron generation and surface phenomena are challenging questions in the surface science and catalysis community. Hot electron flow generated on a gold thin film by photon absorption (or internal photoemission) appears to be correlated with localized surface plasmon resonance. In this perspective, we outline recent research activities to develop energy conversion devices based on hot electrons and surface plasmons. The chemicurrent or hot electron flows correlate well with the turnover rate of CO oxidation or hydrogen oxidation, measured separately by gas chromatography, suggesting an intrinsic relation between the catalytic reaction and hot electron generation. Photon energy can be directly converted to hot electron flow through the metal semiconductor interface of Pt/TiO2. The flow of hot charge carriers influences the chemistry at the oxide metal interface and the turnover rate in the chemical reaction on metal semiconductor nanostructures. The effect of surface plasmons on the catalytic and photocatalytic activity on metal oxide hybrid nanocatalysts is also highlighted.Graphical Abstract
author_names: Jeong Y Park

Sun Mi Kim

Hyosun Lee

Brundabana Naik
title: Hot Electron and Surface Plasmon Driven Catalytic Reaction in Metal Semiconductor Nanostructures
venue: Catalysis Letters
year: 2014

abstract: Abstract Nonradiative surface plasmon decay produces highly energetic electron hole pairs with desirable characteristics, but the measurement and harvesting of nonequilibrium hot holes remain challenging due to ultrashort lifetime and diffusion length. Here, the direct observation of LSPR driven hot holes created in a Au nanoprism/p GaN platform using photoconductive atomic force microscopy (pc AFM) is demonstrated. Significant enhancement of photocurrent in the plasmonic platforms under light irradiation is revealed, providing direct evidence of plasmonic hot hole generation. Experimental and numerical analysis verify that a confined |E| field surrounding a single Au nanoprism spurs resonant coupling between localized surface plasmon resonance (LSPR) and surface charges, thus boosting hot hole generation. Furthermore, geometrical and size dependence on the extraction of LSPR driven hot holes suggests an optimized pathway for their efficient utilization. The direct visualization of hot hole flow at the nanoscale provides significant opportunities for harnessing the underlying nature and potential of plasmonic hot holes.
author_names: Hyunhwa Lee

Kyoungjae Song

Moonsang Lee

Jeong Y Park
title: In Situ Visualization of Localized Surface Plasmon Resonance Driven Hot Hole Flux
venue: Advanced science
year: 2020

author_names: Jeong Y Park

Sun Mi Kim

Hyosun Lee

Brundabana Naik
title: Hot Electron and Surface Plasmon Driven Catalytic Reaction in Metal Semiconductor Nanostructures
year: 2015

author_names: Sun Mi Kim
title: Surface oxide layer and hot electron and surface plasmon driven catalytic reaction pyomyeon sanhwaceunggwa hasjeonja mic pyomyeonpeulrajeumoni yudohaneun hwahagbaneung yeongu
year: 2014

abstract: Light driven synthesis of plasmonic metal nanostructures has garnered broad scientific interests. Although it has been widely accepted that surface plasmon resonance (SPR) generated energetic electrons play an essential role in this photochemical process, the exact function of plasmon generated hot holes in regulating the morphology of nanostructures has not been fully explored. Herein, we discover that those hot holes work with surface adsorbates collectively to control the anisotropic growth of gold (Au) nanostructures. Specifically, it is found that hot holes stabilized by surface adsorbed iodide enable the site selective oxidative etching of Au0, which leads to non uniform growths along different lateral directions to form six pointed Au nanostars. Our studies establish a molecular level understanding of the mechanism behind the plasmon driven synthesis of Au nanostars and illustrate the importance of cooperation between charge carriers and surface adsorbates in regulating the morphology evolution of plasmonic nanostructures.
author_names: Wenxiao Guo

Aaron C Johnston-Peck

Yuchao Zhang

Yue Hu

Jiawei Huang

Wei David Wei
title: Cooperation of Hot Holes and Surface Adsorbates in Plasmon Driven Anisotropic Growth of Gold Nanostars.
venue: Journal of the American Chemical Society
year: 2020