1. Photophysical Effects behind the Efficiency of Hot Electron Injection in Plasmon-Assisted Catalysis: The Joint Role of Morphology and Composition
- Author
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Larousse Khosravi Khorashad, Yoel Negrín-Montecelo, Miguel Comesaña-Hermo, Miguel A. Correa-Duarte, Alexander O. Govorov, Zhiming Wang, Tim Liedl, Ana Sousa-Castillo, Moisés Pérez-Lorenzo, Departamento de Quimica Fisica - Universidade de Vigo, Spain, Universidade de Vigo, Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Ohio University, University of Electronic Science and Technology of China (UESTC), and Ludwig-Maximilians-Universität München (LMU)
- Subjects
Morphology (linguistics) ,Materials science ,Band gap ,Energy Engineering and Power Technology ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,7. Clean energy ,Catalysis ,ACS Energy Lett 2020 ,395−402 ,Materials Chemistry ,[CHIM]Chemical Sciences ,Joint (geology) ,Plasmon ,Hot-carrier injection ,[PHYS]Physics [physics] ,Renewable Energy, Sustainability and the Environment ,business.industry ,[CHIM.CATA]Chemical Sciences/Catalysis ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Fuel Technology ,Semiconductor ,Chemistry (miscellaneous) ,Optoelectronics ,0210 nano-technology ,business ,Visible spectrum - Abstract
International audience; Plasmonic materials are intensively used to extend the photoactivity of large bandgap semiconductors into the visible light region. In this framework, the present study examines the joint role played by the morphology and composition of plasmonic nano-particles in their photosensitizing capabilities. The critical influence of these parameters is evidenced by the effect of Au and core−shell Au@Ag nanorods on a TiO 2-driven photochemical probe reaction. In this case, the use of the bimetallic composites leads to a remarkable increase in the photocatalytic activity of the semiconductor compared to that found for the monometallic Au sensitizers. The mechanism behind this observation has then been computed theoretically concluding that, in terms of hot electron injection, the contribution of the transversal modes of the Au@Ag NRs and the low damping of these nanostructures are responsible for the photocatalytic properties reported herein. The great potential of these architectures is confirmed by their notable performance toward photocatalytic hydrogen generation, rendering this approach an appealing strategy in the search for efficient solar-driven energy systems. N oble metal nanoparticles (NPs) present outstanding optical properties given their strong interaction with light in the visible and near-infrared (NIR) ranges of the electromagnetic spectrum. 1 This coupling arises because of the coherent oscillation of conduction electrons of the metallic objects in resonance with the incoming electromagnetic field, an effect known as localized surface plasmon resonance (LSPR). 2 As a result, a short-lived population of charge carriers ("hot" electrons) is created, being thermalized within the crystalline lattice of the metal on the femtosecond time scale. 3,4 Recent reports have shown that the combination of plasmonic objects with acceptor species such as organic molecules or semiconductors can lead to the exchange of charge carriers and hence to the possibility of using such species to drive chemical processes of interest. 5 Along these lines, plasmonic photosensitization has been identified as a promising interaction between a noble metal and a large bandgap semiconductor toward the formation of hybrid photocatalysts with improved efficiencies and broadband activity. 6,7 In this manner, the Schottky barrier created between both materials extends the lifetime of the hot carriers, thus leading to an accumulation of electrons at the conduction band
- Published
- 2020
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