Self-Optimized Catalysts: Hot-Electron Driven Photosynthesis of Catalytic Photocathodes

Kontoleta, Evgenia; Askes, Sven H. C.; Garnett, Erik C.

doi:10.1021/acsami.9b10913

Cited by 15 publications

(16 citation statements)

References 47 publications

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“…The morphology was different from both what was observed in the absence of H 2 PtCl 6 ( Figure S8 ) and the hot electron-deposited Pt species on Au/TiO 2 nanoislands in our previous work. 27 Subsequently, EDS ( Figure 2 f and EDS elemental map in Figure S9 ) and XPS measurements ( Figure 2 g,h) were conducted for the elemental analysis of the material deposited on the Au nanoislands. Samples illuminated for 2 h ( Figure 2 e) were used for the elemental analysis to increase the signal.…”

Section: Resultsmentioning

confidence: 99%

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Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Kontoleta

Tsoukala

Askes

et al. 2020

ACS Appl. Mater. Interfaces

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Hot electrons generated in metal nanoparticles can drive chemical reactions and selectively deposit cocatalyst materials on the plasmonic hotspots, the areas where the decay of plasmons takes place and the hot electrons are created. While hot electrons have been extensively used for nanomaterial formation, the utilization of hot holes for simultaneous cocatalyst deposition has not yet been explored. Herein, we demonstrate that hot holes can drive an oxidation reaction for the deposition of the manganese oxide (MnO x ) cocatalyst on different plasmonic gold (Au) nanostructures on a thin titanium dioxide (TiO 2 ) layer, excited at their surface plasmon resonance. An 80% correlation between the hot-hole deposition sites and the simulated plasmonic hotspot location is showed when considering the typical hot-hole diffusion length. Simultaneous deposition of more than one cocatalyst is also achieved on one of the investigated plasmonic systems (Au plasmonic nanoislands) through the hot-hole oxidation of a manganese salt and the hot-electron reduction of a platinum precursor in the same solution. These results add more flexibility to the use of hot carriers and open up the way for the design of complex photocatalytic nanostructures.

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Section: Resultsmentioning

confidence: 99%

“… 16 , 17 Hot carriers have been already used for a plethora of chemical reactions such as water splitting, 18 − 21 H 2 dissociation, 22 CO oxidation, 23 NH 3 decomposition, 24 reduction of diazonium salts, 25 and synthesis of nanomaterials. 26 , 27 …”

Section: Introductionmentioning

confidence: 99%

Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Kontoleta

Tsoukala

Askes

et al. 2020

ACS Appl. Mater. Interfaces

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“…Among the processes that can be driven by the excitation of plasmonic hot carriers, some can change the plasmonic NC itself, as schematically depicted in Figure b. These include growth by aggregation of metal ions, ,− shrinkage by photoetching, , and growth or accretion of other materials on its surface. − The schematic diagram in Figure b illustrates the fundamental idea behind the HE-directed metal growth, which will depend on the local rate of HE injection and leads to locally induced growth, changing the NC’s shape. This picture of inhomogeneous HE-directed growth contrasts, for instance, with the resulting surface pattern expected from both growth and surface reactions , driven by photoheating.…”

Section: Photoinduced Growth and Chiralitymentioning

confidence: 99%

Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light

et al. 2021

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Plasmonic nanocrystals and their assemblies are excellent tools to create functional systems, including systems with strong chiral optical responses. Here we study the possibility of growing chiral plasmonic nanocrystals from strictly nonchiral seeds of different types by using circularly polarized light as the chirality-inducing mechanism. We present a novel theoretical methodology that simulates realistic nonlinear and inhomogeneous photogrowth processes in plasmonic nanocrystals, mediated by the excitation of hot carriers that can drive surface chemistry. We show the strongly anisotropic and chiral growth of oriented nanocrystals with lowered symmetry, with the striking feature that such chiral growth can appear even for nanocrystals with subwavelength sizes. Furthermore, we show that the chiral growth of nanocrystals in solution is fundamentally challenging. This work explores new ways of growing monolithic chiral plasmonic nanostructures and can be useful for the development of plasmonic photocatalysis and fabrication technologies.

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“…We now assume that the growth is stimulated on the surface locally by the plasmonic HEs. At this moment, we know from recent reports ,,,,− that the position-dependent plasmonic processes can drive surface photochemistry locally in anisotropic NCs. In NCs with complex shapes, ,,,, photochemical processes may occur mostly in the plasmonic hot spots where the electromagnetic field becomes strongly amplified.…”

Section: Introductionmentioning

confidence: 99%

Hot Electrons Generated in Chiral Plasmonic Nanocrystals as a Mechanism for Surface Photochemistry and Chiral Growth

et al. 2020

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The realization of chiral photochemical reactions at the molecular level has proven to be a challenging task, with invariably low efficiencies originating from very small optical circular dichroism signals. On the contrary, colloidal nanocrystals offer a very large differential response to circularly polarized light when designed with chiral geometries. We propose taking advantage of this capability, introducing a novel mechanism driving surface photochemistry in a chiral nanocrystal. Plasmonic nanocrystals exhibit anomalously large asymmetry factors in optical circular dichroism (CD), and the related hot-electron generation shows in turn a very strong asymmetry, serving as a mechanism for chiral growth. Through theoretical modeling, we show that chiral plasmonic nanocrystals can enable chiral surface growth based on the generation of energetic (hot) electrons. Using simple and realistic phenomenological models, we illustrate how this kind of surface photochemistry can be observed experimentally. The proposed mechanism is efficient if it operates on an already strongly chiral nanocrystal, whereas our proposed mechanism does not show chiral growth for initially nonchiral structures in a solution. The asymmetry factors for the chiral effects, driven by hot electrons, exceed the values observed in chiral molecular photophysics at least 10-fold. The proposed chiral-growth mechanism for the transformation of plasmonic colloids is fundamentally different to the traditional schemes of chiral photochemistry at the molecular level.

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Self-Optimized Catalysts: Hot-Electron Driven Photosynthesis of Catalytic Photocathodes

Cited by 15 publications

References 47 publications

Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light

Hot Electrons Generated in Chiral Plasmonic Nanocrystals as a Mechanism for Surface Photochemistry and Chiral Growth

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