Importance of Plasmonic Heating on Visible Light Driven Photocatalysis of Gold Nanoparticle Decorated Zinc Oxide Nanorods

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Abstract

Herein we explore the role of localized plasmonic heat generated by resonantly excited gold (Au) NPs on visible light driven photocatalysis process. Au NPs are deposited on the surface of vertically aligned zinc oxide nanorods (ZnO NRs). The localized heat generated by Au NPs under 532 nm continuous laser excitation (SPR excitation) was experimentally probed using Raman spectroscopy by following the phonon modes of ZnO. Under the resonant excitation the temperature at the surface of the Au-ZnO NRs reaches up to about 300 °C, resulting in almost 6 times higher apparent quantum yield (AQY) for photocatalytic degradation of methylene blue (MB) compared to the bare ZnO NRs. Under solar light irradiation the Au-ZnO NRs demonstrated visible light photocatalytic activity twice that of what was achieved with bare ZnO NRs, while significantly reduced the activation energy required for the photocatalytic reactions allowing the reactions to occur at a faster rate.

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Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine.

Prashant Jain, Kyeong Seok Lee, Ivan El-Sayed … (2006)

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica-gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed ( approximately 40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from approximately 520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the effectiveness of nanoparticles of different sizes for real biomedical applications, size-normalized optical cross-sections or per micron coefficients are calculated. Gold nanorods show per micron absorption and scattering coefficients that are an order of magnitude higher than those for nanoshells and nanospheres. While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorods of high aspect ratio with a larger effective radius.

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Mechanisms and applications of plasmon-induced charge separation at TiO2 films loaded with gold nanoparticles.

Yang Tian, Tetsu Tatsuma (2005)

Plasmon-induced photoelectrochemistry in the visible region was studied at gold nanoparticle-nanoporous TiO(2) composites (Au-TiO(2)) prepared by photocatalytic deposition of gold in a porous TiO(2) film. Photoaction spectra for both the open-circuit potential and short-circuit current were in good agreement with the absorption spectrum of the gold nanoparticles in the TiO(2) film. The gold nanoparticles are photoexcited due to plasmon resonance, and charge separation is accomplished by the transfer of photoexcited electrons from the gold particle to the TiO(2) conduction band and the simultaneous transfer of compensative electrons from a donor in the solution to the gold particle. Besides its low-cost and facile preparation, a photovoltaic cell with the optimized electron mediator (Fe(2+/3+)) exhibits an optimum incident photon to current conversion efficiency (IPCE) of 26%. The Au-TiO(2) can photocatalytically oxidize ethanol and methanol at the expense of oxygen reduction under visible light; it is potentially applicable to a new class of photocatalysts and photovoltaic fuel cells.

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Plasmonic photocatalysis.

Xuming Zhang, Yu Lim Chen, Ru-Shi Liu … (2013)

Plasmonic photocatalysis has recently facilitated the rapid progress in enhancing photocatalytic efficiency under visible light irradiation, increasing the prospect of using sunlight for environmental and energy applications such as wastewater treatment, water splitting and carbon dioxide reduction. Plasmonic photocatalysis makes use of noble metal nanoparticles dispersed into semiconductor photocatalysts and possesses two prominent features-a Schottky junction and localized surface plasmonic resonance (LSPR). The former is of benefit to charge separation and transfer whereas the latter contributes to the strong absorption of visible light and the excitation of active charge carriers. This article aims to provide a systematic study of the fundamental physical mechanisms of plasmonic photocatalysis and to rationalize many experimental observations. In particular, we show that LSPR could boost the generation of electrons and holes in semiconductor photocatalysts through two different effects-the LSPR sensitization effect and the LSPR-powered bandgap breaking effect. By classifying the plasmonic photocatalytic systems in terms of their contact form and irradiation state, we show that the enhancement effects on different properties of photocatalysis can be well-explained and systematized. Moreover, we identify popular material systems of plasmonic photocatalysis that have shown excellent performance and elucidate their key features in the context of our proposed mechanisms and classifications.

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Author and article information

Journal

Journal ID (nlm-ta): Sci Rep

Journal ID (iso-abbrev): Sci Rep

Title: Scientific Reports

Publisher: Nature Publishing Group

ISSN (Electronic): 2045-2322

Publication date (Electronic): 31 May 2016

Publication date Collection: 2016

Volume: 6

Electronic Location Identifier: 26913

Affiliations

[1 ]Chair in Nanotechnology, Sultan Qaboos University , PO Box 17, Al Khoud–123, Oman

[2 ]Institute for Quantum Optics and Quantum Information, Austrian Academy of Sciences, Technikerstraße 21a , A-6020 Innsbruck, Austria

[3 ]Functional Materials Division, Materials and Nano Physics Department, ICT School, KTH Royal Institute of Technology , SE-164 40, Kista, Stockholm, Sweden

Author notes

[a ] tanujjal@ 123456squ.edu.om

[b ] joydeep@ 123456kth.se

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Publisher Item ID: srep26913

DOI: 10.1038/srep26913

PMC ID: 4886257

PubMed ID: 27242172

SO-VID: f16a917a-29aa-409e-95e8-2c69d85ce05f

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This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

Importance of Plasmonic Heating on Visible Light Driven Photocatalysis of Gold Nanoparticle Decorated Zinc Oxide Nanorods

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Most cited references 15

Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine.

Mechanisms and applications of plasmon-induced charge separation at TiO2 films loaded with gold nanoparticles.

Plasmonic photocatalysis.

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