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      Coupling Plasmonic and Cocatalyst Nanoparticles on N–TiO 2 for Visible-Light-Driven Catalytic Organic Synthesis

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          Abstract

          The use of the surface plasmon resonance (SPR) effect of plasmonic metal nanocomposites to promote photocarrier generation is a strongly emerging field for improving the catalytic performance under visible-light irradiation. In this study, a novel plasmonic photocatalyst, AuPt/N–TiO 2, was prepared via a photo-deposition–calcination technique. The Au nanoparticles (NPs) were used herein to harvest visible-light energy via the SPR effect, and Pt NPs were employed as a cocatalyst for trapping the energetic electrons from the semiconductor, leading to a high solar-energy conversion efficiency. The Au 2Pt 2/N–TiO 2 catalyst, herein with the irradiation wavelength in the range 460–800 nm, exhibited a reaction rate ~24 times greater than that of TiO 2, and the apparent quantum yield at 500 nm reached 5.86%, indicative of the successful functionalization of N–TiO 2 by the integration of Au plasmonic NPs and the Pt cocatalyst. Also, we investigated the effects of two parameters, light source intensity and wavelength, in photocatalytic reactions. It is indicated that the as-prepared AuPt/N–TiO 2 photocatalyst can cause selective oxidation of benzyl alcohol under visible-light irradiation with a markedly enhanced selectivity and yield.

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          Surface-Plasmon-Driven Hot Electron Photochemistry

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            An autonomous photosynthetic device in which all charge carriers derive from surface plasmons.

            Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.
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              Plasmon resonant enhancement of photocatalytic water splitting under visible illumination.

              We demonstrate plasmonic enhancement of photocatalytic water splitting under visible illumination by integrating strongly plasmonic Au nanoparticles with strongly catalytic TiO2. Under visible illumination, we observe enhancements of up to 66× in the photocatalytic splitting of water in TiO2 with the addition of Au nanoparticles. Above the plasmon resonance, under ultraviolet radiation we observe a 4-fold reduction in the photocatalytic activity. Electromagnetic simulations indicate that the improvement of photocatalytic activity in the visible range is caused by the local electric field enhancement near the TiO2 surface, rather than by the direct transfer of charge between the two materials. Here, the near-field optical enhancement increases the electron-hole pair generation rate at the surface of the TiO2, thus increasing the amount of photogenerated charge contributing to catalysis. This mechanism of enhancement is particularly effective because of the relatively short exciton diffusion length (or minority carrier diffusion length), which otherwise limits the photocatalytic performance. Our results suggest that enhancement factors many times larger than this are possible if this mechanism can be optimized.
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                Author and article information

                Journal
                Nanomaterials (Basel)
                Nanomaterials (Basel)
                nanomaterials
                Nanomaterials
                MDPI
                2079-4991
                07 March 2019
                March 2019
                : 9
                : 3
                : 391
                Affiliations
                College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China; wangyannan@ 123456nankai.edu.cn (Y.W.); chenyu0870@ 123456gmail.com (Y.C.); houqidong@ 123456nankai.edu.cn (Q.H.); jumeit@ 123456nankai.edu.cn (M.J.)
                Author notes
                [* ]Correspondence: liweizun@ 123456nankai.edu.cn ; Tel.: +86-135-1221-2566
                Article
                nanomaterials-09-00391
                10.3390/nano9030391
                6473962
                30866493
                132bf0fe-7b0c-4aca-a0f8-f7b8762e473a
                © 2019 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 29 January 2019
                : 01 March 2019
                Categories
                Article

                plasmonic photocatalyst,metal nanoparticle,n–tio2,nanocomposites,photocatalytic selective oxidation

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