Angewandte Chemie International Edition
10.1002/anie.202001531
RESEARCH ARTICLE
to excellent yields under solar light irradiation (300 W Xe lamp,
Such diversely active nanocatalosomes show substantially
distinguished and consistently high catalytic performance than the
reported NP-based catalysts owing to the unique bilayer structure.
By this work, we have opened the avenues towards advanced
next-generation metallic-bilayer-based nanoreactors and
extended the scope of their structural and functional tunability by
including controllable intricacies at few-nm scale. By expanding
the utility of solar energy in fueling the nanocatalosomes, this
research will add enormous value to the sustainable development
of the highly functional catalytic chemistry.
2
0.7 W/cm ) (Figure 6). Reaction rates depended on the different
structures of Au-1~4-NCat, showing highest reactivity in the case
of Au-4-NCat and similar to the Au-multilayer NCat (Au-M-NCat),
validating the influence of bilayer/multilayer-confined plasmonic
effect on reaction rates (Figure 6b and Figure S19). In the bilayer
structure of nanocatalosomes, closely located plasmonic units
with narrow interparticle gaps and cavities can form extensively
coupled plasmonic hot-spots which can concentrate high
electromagnetic fields and other plasmon-induced effects such
as: instantaneous production/transfer of hot charge-carriers and
their equilibration with lattice through an electron-phonon coupling
resulting the photothermal increase in localized temperature;[
all these factors together are responsible for solar-light induced
high catalytic activities of nanocatalosomes. In order to
investigate the individual role of photothermal effect, we tested
the folding/unfolding of proteins in the presence of Au-4-NCat
under light irradiation. Under controlled conditions, such protein
denaturation can only be affected upon exposure to high
temperatures; monitoring of this phenomenon can evidence the
localized photothermal effect on Au-4-NCat.[48] In a mixture of
bovine serum albumin (BSA) and Au-4-NCat, the intensity of
46-47]
Acknowledgements
This work was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (MSIP)
(
Grant NRF-2016R1A3B1907559) (I.S.L.).
Keywords: nanocatalyst • hollow nanostructure • bilayer
structure • plasmonic-catalytic material • nano-space
confinement
characteristic fluorescence band at 300-500 nm reduced up to ca.
2
3
7% upon exposing to the NIR laser (785 nm, 0.7 W/cm ) for 25
min (Figure S20). Next, to further evidence the surface-mediated
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3
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2 2 2
singlet oxygen ( O ). For testing the presence of O in the O -
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T.
2
nm, 0.7 W/cm ), we used fluorescence-based singlet oxygen
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bilayer-based hollow-nanostructures: “nanocatalosomes”, as a
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nanoreactors having controllable bilayer-space. In diverse
plasmonic-catalytic nanocatalosomes, bilayer shell having plenty
of few-nm nanogaps/cavities within intershell nanospace is the
key structural feature which endow controllable plasmonic
coupling effect, and efficiently harness broad range of solar light
to generate localized photothermal heating and plasmonic
charge-carriers, highly useful for variety of catalytic reactions. By
implementing suitably customized nanocatalosomes, challenging
acceptorless dehydrogenation reactions of N-heterocycles were
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accomplished with unprecedented rates and TOF (h ) up to ~11
times higher than conventional Pt-AuNR plasmonic catalyst,
under low power solar irradiation; otherwise, such reactions with
conventional catalysts take very long times ( > 24 h) and energy-
intensive harsh thermal conditions (temperatures up to 150 °C).
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[
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up to ~18 s ) and alkynyl annulation reactions with good to
excellent yields in maximum recorded TOFs, reported so far.
1
9
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