Atomically Conformal Metal Laminations on Plasmonic Nanocrystals for Efficient Catalysis

Article abstract of DOI:10.1021/jacs.1c05753

Despite the enormous application potential, methods for conformal few-atomic-layer deposition on colloidal nanocrystals (NCs) are scarce. Similar to the process of lamination, we introduce a confine and shine strategy to homogeneously modify the different surface curvatures of plasmonic NCs with ultrathin conformal layers of diverse catalytic noble metals. This self-limited epitaxial skinlike metal growth harvests the localized surface plasmon resonance to induce reduction chemistry directly on the NC surface, confined inside hollow silica. This strategy avoids any kinetic anisotropic metal deposition. Unlike the conventional thick, anisotropic, and dendritic shells, which show severe nonradiative damping, the skinlike metal lamination preserves the key plasmonic properties of the core NCs. Consequently, the plasmonic-catalytic hybrid nanoreactors can carry out a variety of organic reactions with impressive rates.

Full text of DOI:10.1021/jacs.1c05753

pubs.acs.org/JACS
Communication
Atomically Conformal Metal Laminations on Plasmonic Nanocrystals
for Efficient Catalysis
Anubhab Acharya, Sateesh Dubbu, Sumit Kumar, Nitee Kumari, Yeseul Kim, Sunae So, Taewan Kwon,
Zhipeng Wang, Junbeom Park, Yoon-Kyoung Cho, Junsuk Rho, Sang Ho Oh, Amit Kumar,*
and In Su Lee*
Cite This: J. Am. Chem. Soc. 2021, 143, 10582−10589
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: Despite the enormous application potential, methods for conformal few-atomic-layer deposition on colloidal
nanocrystals (NCs) are scarce. Similar to the process of lamination, we introduce a “confine and shine” strategy to homogeneously
modify the different surface curvatures of plasmonic NCs with ultrathin conformal layers of diverse catalytic noble metals. This self-
limited epitaxial skinlike metal growth harvests the localized surface plasmon resonance to induce reduction chemistry directly on the
NC surface, confined inside hollow silica. This strategy avoids any kinetic anisotropic metal deposition. Unlike the conventional
thick, anisotropic, and dendritic shells, which show severe nonradiative damping, the skinlike metal lamination preserves the key
plasmonic properties of the core NCs. Consequently, the plasmonic−catalytic hybrid nanoreactors can carry out a variety of organic
reactions with impressive rates.
on the core NCs to eliminate any kinetics-directing role8 and
ailoring the surfaces of metal nanocrystals (NCs) can tap
Tinto the wealth of unique physical and chemical (ii) to localize the plasmonic effect on individually isolated
properties.1 Bimetallic core@shell NCs have attracted
NCs by restricting their interparticle interactions, thereby
avoiding any nonspecific reactions.4 Here we introduce the
immense interest because they can harness interfacial synergy
“confine and shine” strategy to homogeneously laminate the
different surface curvatures of plasmonic NCs (e.g., rod,
sphere, cube, trigonal bipyramid, and dodecahedron) with
ultrathin conformal layers (<1 nm) of diverse catalytic noble
metals (e.g., Pt, Pd, Ru, and Rh) (Scheme 1). We apply LSP-
resonant laser irradiation to activate self-limited photochemical
metal reduction chemistry directly on the plasmonic NC inside
hollow silica. This approach utilizes highly localized plasmonic
energy on individually isolated NCs without any undesired
increase in bulk solution reaction rates. In addition, the
isolated NC surface in combination with laser-induced effects
can effectively overcome the anisotropic metal growth. Because
the metallic lamination is ultrathin, the hallmark plasmonic
properties of the NCs remain well-preserved, and the resulting
plasmonic−catalytic nanoreactors carry out a variety of
chemical transformations with high photoconversion efficien-
cies and turnover frequencies (TOFs). The current method-
ology embarks upon the use of light energy and LSPR-induced
chemistry for nanostructure surface manipulation, resulting in
enhanced properties and diverse applications.
from the core and shell counterparts, rendering applications in
catalysis, plasmonics, electronics, displays, and magnetics.2 The
continuous skinlike atomic layers have several advantages such
as maximization of the surface atomic utilization efficiency,
interfacial lattice effects, light-induced energy transfer
processes, and surface-protective effects.3 Combining plas-
monic NCs (e.g., Au, Ag, Cu) with noble transition metals
(e.g., Pt, Pd, Rh, Ru) results in “antenna−reactor” hybrid
systems for efficient localized surface plasmon resonance
(LSPR)-driven catalysis.4 However, it is critical to limit the
thickness of the nonplasmonic light-absorbing dielectric shell
to preserve the characteristic LSPR extinction and efficient
electromagnetic energy funneling on the whole NC surface.4c
Normally, kinetic metal growth results in spatial anisotropies in
growing metal shells, forming dendrites, islands, or grains.5
This is due to several factors such as differential reactivities of
crystalline facets, lattice mismatch/strain, differences in atomic
cohesive energies, the presence of multiple nucleation sites,
and variable densities of surface ligands. Conventional
strategies using high temperatures, metal etching, under-
potential deposition, and so on can reshape, deform, overgrow,
or sinter the NCs, compromising their hallmark plasmonic
characteristics.6 Despite the enormous applied potential, there
is no generalized method to apply diverse atomically thin
conformal metal coatings on different core shapes. We
envisioned using LSPR-induced surface-localized energy trans-
fer to direct the atomic growth selectively on the NC surface.7
The key challenges in developing such a colloidal synthetic
strategy were (i) to create a ligand-free confined environment
To implement our “confine and shine” strategy, we chose
gold nanorods (AuNRs) as typical plasmonic NCs.9 Because of
Received: June 6, 2021
Published: July 2, 2021
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589
© 2021 American Chemical Society
10582

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
Scheme 1. “Confine and Shine” Strategy for [M] Lamination on Plasmonic NCs
Figure 1. (a) TEM image of Pt-laminated AuNRs in hollow silica (Pt-lam-AuNR@hSiO2). (b) TEM image of Pt-lam-AuNR after silica removal.
(c) EELS elemental mapping of Pt-lam-AuNRs. (d, e) HAADF-STEM images of a Pt-lam-AuNR. (f) EDS elemental mapping and line profile for a
Pt-lam-AuNR. (g) Comparative time-course TEM images of Pt growth with ethylene glycol (EG) and ascorbic acid (AA) under laser irradiation
(785 nm, 0.4 W/cm2). Yellow and pink color gradient bars on each TEM image represent the relative atomic percentages of Au (yellow) and Pt
(pink) as measured by EDS. (h) Schematic of the metal growth mechanisms on CTAB-AuNRs and AuNR@h-SiO2 with strong reducing agents
and plasmon-induced photocatalytic atomic layer deposition (ALD) using EG. EGOxidized and EGRadical represent the oxidized and radical forms of
EG, respectively. Mn+ and M0 are the starting and reduced forms of the metal precursor. h+ and e− are the plasmonic charge carriers participating in
the redox reactions.
the presence of curves (on the tips) and flat surfaces (on the
edges) having different crystal facets and varying ligand
densities as well as the repulsive interaction between Pt and
Au, AuNRs are challenging to modify with a homogeneous
thin conformal Pt layerrather, Pt-on-Pt anisotropic cluster-
ing usually occurs.5 First, to access the individually isolated
AuNRs, we synthesized rattlelike hollow structures having only
a single AuNR (aspect ratio 2.7 0.3) surrounded by a hollow
silica shell (ca. 80 nm) (denoted as AuNR@h-SiO2) and
confirmed the removal of surface ligands during the silica-
coating-hollowing process by Fourier transform infrared
spectroscopy (FTIR) (Figure S1).10 Next, a dispersion of
AuNR@h-SiO2 (1 mg/mL) and Na2PtCl4 (0.5 mL, 50 mM) in
ethylene glycol (EG) (10 mL) was exposed to near-infrared
(NIR) laser irradiation (0.4 W/cm2) at the ambient bulk
solution temperature (35 °C). Transmission electron micros-
copy (TEM) of the resulting Pt-laminated AuNRs (Pt-lam-
AuNRs) revealed a slight increase (<1 nm) in the overall size
of the original AuNRs due to the conformal Pt deposition (ca.
two or three Pt atomic layers) without any measurable change
in the aspect ratio (Figure 1a,b and Table S1). Electron energy
loss spectroscopy (EELS)-based Au/Pt mapping verified the
peripheral Pt atomic layers around the AuNRs (Figure 1c).
High-resolution TEM (HRTEM) and high-angle annular dark-
10583
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
field scanning TEM (HAADF-STEM) affirmed the nanorods
to be monocrystalline, devoid of any newly emerged grain
boundary or anisotropy on either flat or curved surfaces
(Figure 1d,e). Atomic-level-resolved STEM-based energy-
dispersive X-ray spectroscopy (STEM-EDS) elemental map-
ping and line profiling confirmed atomically conformal
epitaxial arrangement of Pt atoms stacked on Au atoms
(Figure 1f). In addition, X-ray diffraction (XRD) and X-ray
photoelectron spectroscopy (XPS) confirmed the chemical
species in Pt-lam-AuNRs (Figures S2 and S3). The XPS Pt 4f
peaks of the Pt-lam-AuNRs showed a decrease in binding
energy (ΔE = 0.73 eV) compared with a thicker Pt shell (ca. 3
nm) on AuNRs (Pt-shell-AuNRs), indicating facile charge
transfer between Au and a larger fraction of Pt in the former
case.11 The presence of a thin Pt skin was also verified after the
Au cores were etched away from Pt-shell-AuNRs (Figure S4).
Oxygen-free conditions did not influence the Pt lamination,
ruling out the indirect oxidative activation of EG by in situ-
produced singlet oxygen (Figure S5).12 Also, Pt lamination did
not proceed in deionized water (DI) in place of EG, indicating
that there was no direct laser-induced reduction of Pt(II) on
AuNRs (Figure S6).13 Moreover, the use of a stronger
reducing agent such as ascorbic acid, hydrazine, or hydroxyl-
amine resulted in conventional branched or dendritic excess
growth of Pt around the AuNRs (Figures 1g and S7).5 In a
comparative TEM time-course study with ascorbic acid,
dendritic Pt growth started at a very early stage (within 1
min) and filled the whole interior volume of h-SiO2, showing
similar results in the presence or absence of laser irradiation
(Figures 1g and S8). In contrast, with EG no such excess
growth of Pt was observed, resulting only in Pt-lam-AuNRs
(∼5 atom % Pt, analyzed for 100 particles by EDS) in 30 min,
even when higher amounts of Pt precursors were used,
indicating the self-limiting nature of the Pt growth (Figure S9).
Also, Pt lamination did not proceed without laser irradiation at
room temperature (Figure S10). The use of conventional
thermal conditions (bulk solution temperature of 50−90 °C)
or high laser fluxes (>1.0 W/cm2) resulted in granular Pt
spilled all over the AuNR@h-SiO2 as a result of nonspecific
thermal polyol reduction (Figures S11 and S12).14 The strong
reductants largely conducted seed-mediated self-catalytic Pt-
on-Pt fast kinetic metal growth, depending on the supply of the
Pt precursor and the reaction time. Distinctly, LSPR-induced
EG-mediated Pt lamination is highly localized and self-limited
only to the availability of bare Au surface. We conducted
electron spin resonance (ESR)-based studies, which evidenced
the presence of EG radicals upon laser irradiation of a solution
of AuNR@h-SiO2 in EG (details are provided in SI section
2.20 and Figure S13). Also, in an FTIR-based study, we
identified an oxidized aldehyde form of EG produced upon
laser irradiation in the presence of AuNR@h-SiO2 (Figure
S14). In contrast, the solution of Pt-lam-AuNR@h-SiO2 in EG
after laser irradiation showed a very weak ESR response
(Figure S13). These results suggested that Pt lamination on
AuNRs is accompanied by LSPR-induced photocatalytic
oxidation of EG through a radical intermediate and is self-
limited after full occupation of the Au surface with a few Pt
atomic layers. Replacing EG with more reactive hole acceptors
such as ethanol and isopropanol resulted granular Pt growth
(Figure S15).14−16 However, other polyols such as diethylene
glycol and triethylene glycol acted similar to EG (Figure S16).
A photothermal heat flux simulation using COMSOL software
(details are provided in SI section 2.29) estimated a very low
photothermal increase in the surface temperatures (ΔT =
16.32 and 14.23 K for AuNRs and Pt-lam-AuNRs,
respectively) under continuous-wave (CW) laser irradiation
at mild power (Figure S17), which is unlikely to induce any
thermal polyol reduction. Replacing the NIR laser (LSPR-
resonant) with a blue laser (352 nm) resulted in the formation
of a bumpy Pt layer on the AuNRs (ca. 12 wt % Pt), indicating
the possibility of utilizing interband transitions for Pt
photodeposition (Figure S18).17 Overall, these results
suggested the dominant LSPR-induced photochemical path-
way for Pt deposition in the presence of EG. LSPR-induced
surface-charge/field redistribution may not only induce
surface-selective photocatalytic Pt deposition but also assist
in conformal organization of the Pt atoms while avoiding Pt
overgrowth and clustering.18
To gain insight into the origin of the uniform conformal
nature of the Pt layer, we synthesized tiny Pt grains directly
interfaced with the AuNRs and irradiated the nanoparticles
(NPs) with the NIR laser (details are provided in SI section
2.25 and Figures S19 and S20). A time-course study based on
HRTEM and HAADF-STEM revealed the deformation and
fusion of Pt grains on the Au surface to form a uniform Pt layer
(Figure S20). This suggested a possible contribution of laser-
induced declustering of Pt atoms during EG-mediated
photochemical deposition of few-layer Pt. In Pt-lam-AuNR@
h-SiO2, there was no structural reorganization of the
presynthesized Pt layer into clusters after laser treatment
(Figure S21), indicating the high stability of the Au−Pt
interfacial structure.19 When we attempted Pt lamination on
cetyltrimethylammonium bromide (CTAB)-coated AuNRs
(CTAB-AuNRs) dispersed in EG, severe aggregation of the
AuNRs was noticed (Figure S22), and Pt growth was found to
originate at the tips because of the lower ligand density,
followed by granular growth along the edges (Figure S23).5 In
AuNR@h-SiO2, the ligand-free surface helped to overcome any
ligand-induced anisotropic/clusterlike metal growth (Figure
S24). Apart from ensuring colloidal stability of the bare
AuNRs, optically transparent h-SiO2 kept individual AuNRs
isolated from each other to avoid any interparticle plasmonic
coupling and NC fusion/welding upon laser irradiation (Figure
S25).20
Next, we generalized our metal lamination strategy by
conducting the growth of other extensively useful catalytic
metals (M = Pd, Ru, Rh) on AuNR@h-SiO2 using the
Na2PdCl4/EG, RuCl3/formaldehyde, and RhCl3/hydroqui-
none (metal precursor/reducing agent), respectively, resulting
in different ultrathin conformal M laminations on AuNRs
(Figures S26 and S27). In the latter two cases, stronger
reducing agents were necessary because of the lower redox
potentials of Ru (E°redox = 0.46 V vs NHE) and Rh (E°redox
=
0.76 V vs NHE).21 Furthermore, we extended the “confine and
shine” strategy to other plasmonic NC shapes such as Au
spheres, cubes, trigonal bipyramids, and dodecahedra individ-
ually located inside h-SiO2 using a resonant green laser (532
nm, 32 mW/cm2) (Figure S28). When a mixture of AuNR@h-
SiO2 and other plasmonic NC shapes (AuNC@h-SiO2) was
subjected to Pt lamination using an NIR laser, Pt growth took
place only on the AuNRs, with no reaction on other AuNC
shapes (Figure S29). Such selective resonant-wavelength-
dependent M lamination chemistry validated the crucial
LSPR-mediated activation mechanism.
We recorded UV−vis absorption spectra of Pt-lam-AuNR@
h-SiO2, which showed that the absorption at 785 nm is still
10584
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
Figure 2. Characterized and simulated plasmonic properties of AuNRs, Pt-lam-AuNRs, and Pt-shell-AuNRs. (a) Digital photographs and UV−vis
spectra. (b) IR camera images and photothermal conversions with an NIR laser (785 nm, 2 W/cm2). (c) Simulated electric field distributions based
on finite-element method (FEM) and (d) SERS spectra of Rh6G modified on NC surfaces. (e) Representative dark-field microscopy images: (top)
AuNR@h-SiO2 before (left) and after (right) Pt lamination; (bottom) CTAB-AuNRs before (left) and after (right) dispersion in EG. The insets
show light intensity profiles on single spots. (f, g) Quantification of bright spots and particle aggregation through dark-field microscopy in each case
(details are provided in SI section 2.17).
much stronger than the absorption at 532 nm, with only a
slight broadening and suppression of the characteristic
longitudinal LSPR absorption due to the minimal change in
the dielectric environment resulting from the ultrathin Pt
atomic layer (Figure 2a).5 However, in the case of a thicker Pt
shell (Pt-shell-AuNR@h-SiO2), the LSPR band at 785 nm was
suppressed dramatically, indicating poor absorption in the NIR
region. Also, the photothermal conversions by Pt-lam-AuNR@
h-SiO2 and AuNR@h-SiO2 were similar (ΔT ≈ 32 °C with 785
nm laser irradiation at 2 W/cm2) (Figures 2b and S30).
Surface-enhanced Raman scattering (SERS) was also found to
be highly sensitive to the LSPR properties: the characteristic
peak intensities of rhodamine 6G modified on AuNR@h-SiO2
and Pt-lam-AuNR were comparable, but that on Pt-shell-
AuNR@h-SiO2 was dramatically decreased (Figure 2d). Finite-
element method (FEM)-based COMSOL simulation on a Pt-
shell-AuNR model (2.2 nm thick Pt shell) estimated a drastic
9.2-fold decrease in the extinction at 785 nm and consequently
in the electric field compared with that of a AuNR (Figure 2c
and Tables S2 and S3), suggesting a nonradiative damping
effect of the Pt shell. Using dark-field microscopy, we studied
interparticle interactions of different NPs (AuNR@h-SiO2, Pt-
lam-AuNR@h-SiO2, and CTAB-AuNR dispersed in EG with
Na2PtCl4). The light scattering intensities of AuNR@h-SiO2
and Pt-lam-AuNR@h-SiO2 remained similar and consistent up
to 30 min, but CTAB-AuNRs showed significant aggregation
within 5 min (Figure 2e−g). This validated the key role of the
h-SiO2 confiner in maintaining sufficient interparticle separa-
tion and hindering any undesired plasmonic coupling due to
NC aggregation.
We measured the electrochemically active surface area
(ECSA) of different NPs (details are provided in SI section
2.27).22 The estimated mass-normalized ECSA of Pt-lam-
AuNRs (61.59 m2/g) was found to be 4 times higher than that
of Pt-shell-AuNRs (16.17 m2/g) (Figure S31). In M-lam-
AuNR@h-SiO2, the ultrathin M layer exposes a high number
of catalytic metal sites, and the protective porous h-SiO2
enclosure constructed a nanoreactor platform to carry out
chemical reactions.23 As a proof of application, we tested Pt-
lam-AuNR@h-SiO2 for Pt-catalyzed conversion of nonfluor-
escent N-pentynoyl-protected rhodamine 110 (pro-Rh-110) (1
mg/mL in H2O/DMSO) to green-fluorescent rhodamine 110
(Rh-110) with NIR laser irradiation (785 nm, 0.4 W/cm2) at
the bulk solution temperature (<40 °C) (Figure 3a).24 The
reaction resulted in the emergence of green fluorescence due to
the production of free Rh-110 with >99% conversion (TOF =
0.53 min−1) within 1 h (Figure 3b). Dark conditions did not
result any measurable change in fluorescence at low temper-
atures (<40 °C), whereas raising the temperature of the
reaction to 85 °C with an oil bath afforded ∼95% conversion
within 1 h (Figure 3c). This result signified that the reaction
can also be thermally induced at much higher temperatures.
Under an identical laser flux, Pt-shell-AuNR@h-SiO2 afforded
∼26 times slower conversion (TOF = 0.02 min−1) relative to
Pt-lam-AuNR@h-SiO2. Such a stark difference in reaction
rates may be attributed to the suppressed LSPR extinction due
10585
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
Figure 3. Catalytic properties of Pt-lam-AuNR@h-SiO2 for decaging of N-pentynoyl-Rh-110. (a) Schematic of the Pt-catalyzed decaging reaction.
(b) Fluorescence spectra for the reactions catalyzed by Pt-lam-AuNR@h-SiO2 and Pt-shell-AuNR@h-SiO2. (c) Time-dependent change in
fluorescence of the reaction mixture under different conditions. (d) Comparison of TOF values for different catalysts. (e) Substrate scope for the
catalytic reaction. (f) TEM images of different control catalysts. (g) Bright-field and fluorescence images showing intracellular catalysis in MCF-7
cells incubated with Pt-lam-AuNR@h-SiO2.
to the thick Pt shell and consequently the weaker plasmon-
induced effect in the case of Pt-shell-AuNR@h-SiO2. Also,
AuNR@h-SiO2 showed no reactivity, validating the indispen-
sable catalytic role of the outermost [Pt] layer.24 In addition,
Pt-shell@h-SiO2 (without Au content) showed no reaction
upon NIR irradiation (Figure 3d,f). These results deconvo-
luted the synergistic roles of the plasmonic and catalytic
components, viz., the AuNR and ultrathin Pt layer,
respectively. A mixture of AuNR@h-SiO2 and Pt-shell@h-
SiO2 (having plasmonic and catalytic components in separate
h-SiO2 confiners) showed no reaction upon NIR irradiation,
ruling out any interparticle energy transfer process and
validating the fact that the plasmonic effect remained highly
localized. Interestingly, Pt grains on AuNRs inside h-SiO2 (Pt-
grain-AuNR@h-SiO2) showed a ca. 3.5 times lower reaction
rate (TOF = 0.15 min−1) than Pt-lam-AuNR@h-SiO2 (Figure
3d,f), vindicating the intimate and extensively interfacial Pt
lamination for efficient plasmonic energy flow to the surface Pt
catalytic sites. The intimate fusion and adhesion of Pt atoms on
the AuNR makes the catalytic surface in Pt-lam-AuNR highly
robust, as was verified by the recyclability test using the same
catalyst in multiple cycles (10 cycles) without any loss in
activity (Figure S32). However, silica-free Pt-lam-AuNRs and
Pt-grain-AuNRs showed reduced conversion yields of 68% and
14%, respectively (Figure S33), possibly due to NP-
aggregation-mediated loss of catalytic activity. These experi-
ments suggested an LSPR-induced catalytic mechanism in
which plasmonic energy can be efficiently transferred to surface
catalytic sites.25 Under the CW laser irradiation (0.4 W/cm2),
the negligible photothermal temperature increase (Figure S17)
is unlikely to increase the reaction rates.
To obtain supporting evidence for the involvement of charge
carriers during catalysis, we performed the direct reduction of
methylene blue (MB) to MB radical ion (MBred) and affirmed
efficient reaction in the case of Pt-lam-AuNRs (SI section 2.26
and Figure S34).25a We also investigated the generation and
dynamics of hot charge carriers by transient absorption (TA)
spectroscopy (SI section 2.19 and Figure S35).26 The hot
electron generation efficiency (ΔODmax/OD) of Pt-lam-
AuNRs was found to be much higher than that of Pt-shell-
AuNRs but slightly lower than that of AuNRs, and the excited
charge carrier lifetime (τ) was found to be 2.94 ps, which was
slightly lower than that of the AuNRs (3.8 ps). Evidently, the
higher excited charge carrier generation efficiency and longer
lifetime in the case of Pt-lam-AuNRs are critical for more
efficient plasmonic energy flow, which in turn resulted in
10586
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
higher catalytic efficacy (Figures 3e and S36−S40). Other
LSPR-induced reactions such as Pd-catalyzed Suzuki−Miyaura
and Heck C−C cross-couplings (Figure S41) and Pt-catalyzed
reduction of nitroarenes (Figure S42) were also successfully
carried out using Pd-lam-AuNR@h-SiO2 and Pt-lam-AuNR@
h-SiO2, respectively (details are provided in SI sections 2.11
and 2.12).
The efficient LSPR-induced catalysis at physiological bulk
temperature with remotely operable NIR light coupled with
the biocompatibility, chemical inertness, and optical trans-
parency of h-SiO2 enclosure motivated us to utilize our
nanoreactors for intracellular catalysis.27 MCF-7 cells were
incubated with Pt-lam-AuNR@h-SiO2, followed by treatment
with N-pentynoyl-Rh-110. Thereafter, upon NIR-light irradi-
ation of the selected population of the cells, the emergence of
green fluorescence was observed in the intracellular regions,
confirming the generation of free Rh-110 (Figure 3g). Well-
protected from the reach of large-sized complex biomolecules
by h-SiO2, the ultrathin Pt layer on the AuNRs not only helps
to efficiently induce new-to-nature chemical reactions on
demand with remotely operable nondamaging low laser powers
but also minimizes the use of cytotoxic but catalytically
versatile metals such as Pt.
In summary, we have devised a “confine and shine” strategy
to modify ligand-free plasmonic NCs with atomically
conformal layers of different noble transition metals by
investing in LSPR-induced surface-centric and self-limited
metal deposition chemistry. Our approach overcomes the
bottlenecks of conventional metal growth methods, which are
guided by complex reaction kinetic parameters, often resulting
in heterogeneous and uncontrollable metal growth. Extensively
useful LSPR-based properties remain well-preserved because of
the ultrathin skinlike atomic lamination of nonplasmonic
metals. The metal lamination process transforms the chemi-
cally inert Au surface into a highly functional catalytic platform
that can be used to carry out a variety of light-induced
chemical reactions with impressive TOFs. We have demon-
strated the potential of our nanoreactor platform for bio-
orthogonal catalysis. Distinguished from the conventional
nanomaterials synthesis approaches, our platform-based
strategy provides inspiration to synergistically merge different
paradigms of nanoscale properties, leading to applications in
catalysis, sustainable energy conversion, biotechnology, and
biomedical science.
Korea; orcid.org/0000-0002-2588-1444;
Email: insulee97@postech.ac.kr
Amit Kumar − Creative Research Initiative Center for
Nanospace-Confined Chemical Reactions (NCCR) and
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, Korea;
orcid.org/0000-0001-7260-3044; Email: amitkumar@
postech.ac.kr
Authors
Anubhab Acharya − Creative Research Initiative Center for
Nanospace-Confined Chemical Reactions (NCCR) and
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, Korea
Sateesh Dubbu − Creative Research Initiative Center for
Nanospace-Confined Chemical Reactions (NCCR) and
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, Korea
Sumit Kumar − Center for Soft and Living Matter, Institute
for Basic Science (IBS), and Department of Biomedical
Engineering, School of Life Sciences, Ulsan National Institute
of Science and Technology (UNIST), Ulsan 44919, Korea
Nitee Kumari − Creative Research Initiative Center for
Nanospace-Confined Chemical Reactions (NCCR) and
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, Korea
Yeseul Kim − Department of Mechanical Engineering, Pohang
University of Science and Technology (POSTECH), Pohang
37673, Korea
Sunae So − Department of Mechanical Engineering, Pohang
University of Science and Technology (POSTECH), Pohang
37673, Korea
Taewan Kwon − Creative Research Initiative Center for
Nanospace-Confined Chemical Reactions (NCCR) and
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, Korea
Zhipeng Wang − Department of Energy Science,
Sungkyunkwan University (SKKU), Suwon 16419, Korea
Junbeom Park − Department of Chemistry, Pohang University
of Science and Technology (POSTECH), Pohang 37673,
Korea
Yoon-Kyoung Cho − Center for Soft and Living Matter,
Institute for Basic Science (IBS), and Department of
Biomedical Engineering, School of Life Sciences, Ulsan
National Institute of Science and Technology (UNIST),
Ulsan 44919, Korea; orcid.org/0000-0001-6423-1834
Junsuk Rho − Department of Mechanical Engineering and
Department of Chemical Engineering, Pohang University of
Science and Technology (POSTECH), Pohang 37673,
Korea; orcid.org/0000-0002-2179-2890
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.1c05753.
Sang Ho Oh − Department of Energy Science, Sungkyunkwan
Materials and methods, additional TEM images, XRD
patterns, XPS spectra, NMR spectra, and simulation
details (PDF)
University (SKKU), Suwon 16419, Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.1c05753
AUTHOR INFORMATION
■
Notes
Corresponding Authors
The authors declare no competing financial interest.
In Su Lee − Creative Research Initiative Center for Nanospace-
Confined Chemical Reactions (NCCR) and Department of
Chemistry, Pohang University of Science and Technology
(POSTECH), Pohang 37673, Korea; Institute for
Convergence Research and Education in Advanced
Technology (I-CREATE), Yonsei University, Seoul 03722,
ACKNOWLEDGMENTS
■
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
10587
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
Single Colloidal Platinum Nanocrystal Growth Trajectories. Science
2009, 324, 1309−1312.
Planning (MSIP) (Grants NRF-2016R1A3B1907559 to I.S.L.
and NRF-2020R1I1A1A01071721 to A.K.).
(6) (a) Vara, M.; Roling, L. T.; Wang, X.; Elnabawy, A. O.; Hood, Z.
D.; Chi, M.; Mavrikakis, M.; Xia, Y. Understanding the Thermal
Stability of Palladium−Platinum Core−Shell Nanocrystals by In Situ
Transmission Electron Microscopy and Density Functional Theory.
ACS Nano 2017, 11, 4571−4581. (b) Guo, X.; Zhang, Q.; Sun, Y.;
Zhao, Q.; Yang, J. Lateral Etching of Core−Shell Au@Metal
Nanorods to Metal-Tipped Au Nanorods with Improved Catalytic
Activity. ACS Nano 2012, 6, 1165−1175. (c) Ithurria, S.; Talapin, D.
V. Colloidal Atomic Layer Deposition (c-ALD) Using Self-Limiting
Reactions at Nanocrystal Surface Coupled to Phase Transfer between
Polar and Nonpolar Media. J. Am. Chem. Soc. 2012, 134, 18585−
18590. (d) Carino, E. V.; Crooks, R. M. Characterization of Pt@Cu
Core@Shell Dendrimer-Encapsulated Nanoparticles Synthesized by
Cu Underpotential Deposition. Langmuir 2011, 27, 4227−4235.
(e) Mohamed, M. B.; Ismail, K. Z.; Link, S.; El-Sayed, M. A. Thermal
Reshaping of Gold Nanorods in Micelles. J. Phys. Chem. B 1998, 102,
9370−9374.
(7) (a) Kamarudheen, R.; Kumari, G.; Baldi, A. Plasmon-Driven
Synthesis of Individual Metal@semiconductor Core@shell Nano-
particles. Nat. Commun. 2020, 11, 3957. (b) Jin, R.; Charles Cao, Y.;
Hao, E.; Métraux, G. S.; Schatz, G. C.; Mirkin, C. A. Controlling
Anisotropic Nanoparticle Growth through Plasmon Excitation. Nature
2003, 425, 487−490.
(8) (a) Kumar, A.; Jeon, K.-W.; Kumari, N.; Lee, I. S. Spatially
Confined Formation and Transformation of Nanocrystals within
Nanometer-Sized Reaction Media. Acc. Chem. Res. 2018, 51, 2867−
2879. (b) Wang, X.; Feng, J.; Bai, Y.; Zhang, Q.; Yin, Y. Synthesis,
Properties, and Applications of Hollow Micro-/Nanostructures.
Chem. Rev. 2016, 116, 10983−11060. (c) Li, Y.; Shi, J. Hollow−
Structured Mesoporous Materials: Chemical Synthesis, Functionaliza-
tion and Applications. Adv. Mater. 2014, 26, 3176−3205. (d) Lian, J.;
Xu, Y.; Lin, M.; Chan, Y. Aqueous-Phase Reactions on Hollow Silica-
Encapsulated Semiconductor Nanoheterostructures. J. Am. Chem. Soc.
2012, 134, 8754−8757.
REFERENCES
■
(1) (a) Jiang, L.; Liu, K.; Hung, S.-F.; Zhou, L.; Qin, R.; Zhang, Q.;
Liu, P.; Gu, L.; Chen, H. M.; Fu, G.; Zheng, N. Facet Engineering
Accelerates Spillover Hydrogenation on Highly Diluted Metal
Nanocatalysts. Nat. Nanotechnol. 2020, 15, 848−853. (b) Ghosh, S.;
Roy, P.; Karmodak, N.; Jemmis, E. D.; Mugesh, G. Nanoisozymes:
Crystal-Facet-Dependent Enzyme-Mimetic Activity of V2O5 Nano-
materials. Angew. Chem., Int. Ed. 2018, 57, 4510−4515.
(2) (a) Li, Z.; Jin, J.; Yang, F.; Song, N.; Yin, Y. Coupling Magnetic
and Plasmonic Anisotropy in Hybrid Nanorods for Mechanochromic
Responses. Nat. Commun. 2020, 11, 2883. (b) Xie, X.; Gao, N.; Deng,
R.; Sun, Q.; Xu, Q.-H.; Liu, X. Mechanistic Investigation of Photon
Upconversion in Nd3+-Sensitized Core−Shell Nanoparticles. J. Am.
Chem. Soc. 2013, 135, 12608−12611. (c) Kobayashi, H.; Yamauchi,
M.; Kitagawa, H.; Kubota, Y.; Kato, K.; Takata, M. Hydrogen
Absorption in the Core/Shell Interface of Pd/Pt Nanoparticles. J. Am.
Chem. Soc. 2008, 130, 1818−1819.
(3) (a) Wang, G.; Huang, B.; Xiao, L.; Ren, Z.; Chen, H.; Wang, D.;
̃
Abruna, H. D.; Lu, J.; Zhuang, L. Pt Skin on AuCu Intermetallic
Substrate: a Strategy to Maximize Pt Utilization for Fuel Cells. J. Am.
Chem. Soc. 2014, 136, 9643−9649. (b) Henning, A. M.; Watt, J.;
Miedziak, P. J.; Cheong, S.; Santonastaso, M.; Song, M.; Takeda, Y.;
Kirkland, A. I.; Taylor, S. H.; Tilley, R. D. Gold−Palladium Core−
Shell Nanocrystals with Size and Shape Control Optimized for
Catalytic Performance. Angew. Chem., Int. Ed. 2013, 52, 1477−1480.
(c) Wang, J. X.; Inada, H.; Wu, L.; Zhu, Y.; Choi, Y.; Liu, P.; Zhou,
W.-P.; Adzic, R. R. Oxygen Reduction on Well-Defined Core−Shell
Nanocatalysts: Particle Size, Facet, and Pt Shell Thickness Effects. J.
Am. Chem. Soc. 2009, 131, 17298−17302. (d) Stamenkovic, V. R.;
Mun, B. S.; Mayrhofer, K. J. J.; Ross, P. N.; Markovic, N. M. Effect of
Surface Composition on Electronic Structure, Stability, and Electro-
catalytic Properties of Pt-transition Metal Alloys: Pt-skin versus Pt-
skeleton Surfaces. J. Am. Chem. Soc. 2006, 128, 8813−8819.
(9) (a) Mackey, M. A.; Ali, M. R. K.; Austin, L. A.; Near, R. D.; El-
Sayed, M. A. The Most Effective Gold Nanorod Size for Plasmonic
Photothermal Therapy: Theory and In Vitro Experiments. J. Phys.
Chem. B 2014, 118 (5), 1319−1326. (b) Gole, A.; Murphy, C. J.
Seed-Mediated Synthesis of Gold Nanorods: Role of the Size and
Nature of the Seed. Chem. Mater. 2004, 16, 3633−3640.
(4) (a) Sousa-Castillo, A.; Couceiro, J. R.; Tomás-Gamasa, M.;
Marin
̃
o-López, A.; López, F.; Baaziz, W.; Ersen, O.; Comesan
̃
a-
Hermo, M.; Mascaren
̃
as, J. L.; Correa-Duarte, M. A. Remote
Activation of Hollow Nanoreactors for Heterogeneous Photocatalysis
in Biorelevant Media. Nano Lett. 2020, 20, 7068−7076. (b) Zhou, L.;
Swearer, D. F.; Zhang, C.; Robatjazi, H.; Zhao, H.; Henderson, L.;
Dong, L.; Christopher, P.; Carter, E. A.; Nordlander, P.; Halas, N. J.
Quantifying Hot Carrier and Thermal Contributions in Plasmonic
Photocatalysis. Science 2018, 362, 69−72. (c) Aslam, U.; Chavez, S.;
Linic, S. Controlling Energy Flow in Multimetallic Nanostructures for
Plasmonic Catalysis. Nat. Nanotechnol. 2017, 12, 1000−1005.
(10) (a) Gorelikov, I.; Matsuura, N. Single-Step Coating of
Mesoporous Silica on Cetyltrimethyl Ammonium Bromide-Capped
Nanoparticles. Nano Lett. 2008, 8, 369−373. (b) Zhu, Z.; Zhang, S.;
Li, C.; Zhang, J.; Yu, J.; Du, X.; He, L.; Zhang, X. A Mechanistic Study
of Silica-Etching by Hot Water. Phys. Chem. Chem. Phys. 2018, 20,
1440−1446. (c) Wong, Y. J.; Zhu, L.; Teo, W. S.; Tan, Y. W.; Yang,
(5) (a) Guo, J.; Zhang, Y.; Shi, L.; Zhu, Y.; Mideksa, M. F.; Hou, K.;
Zhao, W.; Wang, D.; Zhao, M.; Zhang, X.; Lv, J.; Zhang, J.; Wang, X.;
Tang, Z. Boosting Hot Electrons in Hetero-Superstructures for
Plasmon-Enhanced Catalysis. J. Am. Chem. Soc. 2017, 139, 17964−
17972. (b) Huang, H.; Zhang, L.; Lv, Z.; Long, R.; Zhang, C.; Lin, Y.;
Wei, K.; Wang, C.; Chen, L.; Li, Z.-Y.; Zhang, Q.; Luo, Y.; Xiong, Y.
Unraveling Surface Plasmon Decay in Core−Shell Nanostructures
toward Broadband Light-Driven Catalytic Organic Synthesis. J. Am.
Chem. Soc. 2016, 138, 6822−6828. (c) Grzelczak, M.; Pérez-Juste, J.;
García de Abajo, F. J.; Liz-Marzán, L. M. Optical Properties of
Platinum-Coated Gold Nanorods. J. Phys. Chem. C 2007, 111, 6183−
6188. (d) Tan, S. F.; Bisht, G.; Anand, U.; Bosman, M.; Yong, X. E.;
Mirsaidov, U. In Situ Kinetic and Thermodynamic Growth Control of
Au−Pd Core−Shell Nanoparticles. J. Am. Chem. Soc. 2018, 140,
11680−11685. (e) Straney, P. J.; Diemler, N. A.; Smith, A. M.;
Eddinger, Z. E.; Gilliam, M. S.; Millstone, J. E. Ligand-Mediated
Deposition of Noble Metals at Nanoparticle Plasmonic Hotspots.
Langmuir 2018, 34, 1084−1091. (f) Fennell, J.; He, D.; Tanyi, A. M.;
Logsdail, A. J.; Johnston, R. L.; Li, Z. Y.; Horswell, S. L. A Selective
Blocking Method to Control the Overgrowth of Pt on Au Nanorods.
J. Am. Chem. Soc. 2013, 135, 6554−6561. (g) Zheng, H.; Smith, R. K.;
Jun, Y.; Kisielowski, C.; Dahmen, U.; Alivisatos, A. P. Observation of
̈
Y.; Wang, C.; Chen, H. Revisiting the Stober Method: Inhomogeneity
in Silica Shells. J. Am. Chem. Soc. 2011, 133, 11422−11425. (d) Feng,
J.; Wang, Z.; Shen, B.; Zhang, L.; Yang, X.; He, N. Effects of Template
Removal on Both Morphology of Mesoporous Silica-Coated Gold
Nanorod and Its Biomedical Application. RSC Adv. 2014, 4, 28683−
28690.
(11) Zhang, S.; Zhang, L.; Liu, Z.; Liu, M.; Fan, Q.; Liu, K.; Gao, C.
Robust Synthesis of Ultrathin Au−Ag Nanowires as a High-Surface-
Area, Synergistic Substrate for Constructing Efficient Pt-Based
Catalysts. J. Mater. Chem. A 2018, 6, 22161−22169.
(12) Kumar, A.; Kumar, S.; Rhim, W.-K.; Kim, G.-H.; Nam, J.-W.
Oxidative Nanopeeling Chemistry-Based Synthesis and Photo-
dynamic and Photothermal Therapeutic Applications of Plasmonic
Core-Petal Nanostructures. J. Am. Chem. Soc. 2014, 136, 16317−
16325.
(13) Forcherio, G. T.; Baker, D. R.; Boltersdorf, J.; Leff, A. C.;
McClure, J. P.; Grew, K. N.; Lundgren, C. A. Targeted Deposition of
Platinum onto Gold Nanorods by Plasmonic Hot Electrons. J. Phys.
Chem. C 2018, 122, 28901−28909.
(14) Dong, H.; Chen, Y.-C.; Feldmann, C. Polyol Synthesis of
NanoParticles: Status and Options Regarding Metals, Oxides,
10588
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589

Journal of the American Chemical Society
pubs.acs.org/JACS
Communication
Chalcogenides, and Non-metal Elements. Green Chem. 2015, 17,
4107−4132.
(15) (a) Yu, S.; Mohan, V.; Jain, P. K. Using Plasmonically
Generated Carriers as Redox Equivalents. MRS Bull. 2020, 45 (1),
43−48. (b) Kim, Y.; Smith, J. G.; Jain, P. K. Harvesting Multiple
Electron−Hole Pairs Generated through Plasmonic Excitation of Au
Nanoparticles. Nat. Chem. 2018, 10 (7), 763−769.
(16) Fiévet, F.; Ammar-Merah, S.; Brayner, R.; Chau, F.; Giraud, M.;
Mammeri, F.; Peron, J.; Piquemal, J.-Y.; Sicard, L.; Viau, G. The
Polyol Process: A Unique Method for Easy Access to Metal
Nanoparticles with Tailored Sizes, Shapes and Compositions. Chem.
Soc. Rev. 2018, 47, 5187−5233.
(27) (a) Lee, J.; Dubbu, S.; Kumari, N.; Kumar, A.; Lim, J.; Kim, S.;
Lee, I. S. Magnetothermia-Induced Catalytic Hollow Nanoreactor for
Bioorthogonal Organic Synthesis in Living Cells. Nano Lett. 2020, 20,
6981−6988. (b) Kumar, A.; Kumar, S.; Kumari, N.; Lee, S. H.; Han,
J.; Michael, I. J.; Cho, Y.-K.; Lee, I. S. Plasmonically Coupled
Nanoreactors for NIR-Light-Mediated Remote Stimulation of
Catalysis in Living Cells. ACS Catal. 2019, 9, 977−990. (c) Destito,
P.; Sousa-Castillo, A.; Couceiro, J. R.; López, F.; Correa-Duarte, M.
A.; Mascarenas, J. L. Hollow Nanoreactors for Pd-Catalyzed Suzuki−
̃
Miyaura Coupling and O-Propargyl Cleavage Reactions in Bio-
relevant Aqueous Media. Chem. Sci. 2019, 10, 2598−2603.
(17) (a) Wilson, A. J.; Mohan, V.; Jain, P. K. Mechanistic
Understanding of Plasmon-Enhanced Electrochemistry. J. Phys.
Chem. C 2019, 123, 29360−29369. (b) Zhao, J.; Nguyen, S. C.; Ye,
R.; Ye, B.; Weller, H.; Somorjai, G. A.; Alivisatos, A. P.; Toste, F. D. A
Comparison of Photocatalytic Activities of Gold Nanoparticles
Following Plasmonic and Interband Excitation and a Strategy for
Harnessing Interband Hot Carriers for Solution Phase Photocatalysis.
ACS Cent. Sci. 2017, 3, 482−488. (c) Yu, S.; Wilson, A. J.; Heo, J.;
Jain, P. K. Plasmonic Control of Multi-Electron Transfer and C−C
Coupling in Visible-Light-Driven CO2 Reduction on Au Nano-
particles. Nano Lett. 2018, 18, 2189−2194.
(18) (a) Guo, W.; Johnston-Peck, A. C.; Zhang, Y.; Hu, Y.; Huang,
J.; Wei, W. D. Cooperation of Hot Holes and Surface Adsorbates in
Plasmon-Driven Anisotropic Growth of Gold Nanostars. J. Am. Chem.
Soc. 2020, 142, 10921−10925. (b) Langille, M. R.; Personick, M. L.;
Mirkin, C. A. Plasmon-Mediated Syntheses of Metallic Nanostruc-
tures. Angew. Chem., Int. Ed. 2013, 52, 13910−13940.
(19) (a) He, D. S.; Han, Y.; Fennell, J.; Horswell, S. L.; Li, Z. Y.
Growth and Stability of Pt on Au Nanorods. Appl. Phys. Lett. 2012,
101, 113102. (b) Stolbov, S.; Zuluaga, S. Factors Controlling the
Reactivity of Catalytically Active Monolayers on Metal Substrates. J.
Phys. Chem. Lett. 2013, 4, 1537−1540.
(20) (a) Salmon, A. R.; Kleemann, M.-E.; Huang, J.; Deacon, W. M.;
Carnegie, C.; Kamp, M.; de Nijs, B.; Demetriadou, A.; Baumberg, J. J.
Light-Induced Coalescence of Plasmonic Dimers and Clusters. ACS
Nano 2020, 14, 4982−4987. (b) Garnett, E. C.; Cai, W.; Cha, J. J.;
Mahmood, F.; Connor, S. T.; Greyson Christoforo, M.; Cui, Y.;
McGehee, M. D.; Brongersma, M. L. Self-Limited Plasmonic Welding
of Silver Nanowire Junctions. Nat. Mater. 2012, 11, 241−249.
(21) Shimura, K.; Yoshida, H. Heterogeneous photocatalytic
hydrogen production from water and biomass derivatives. Energy
Environ. Sci. 2011, 4, 2467−2481.
(22) Wang, J.; Heo, J.; Chen, C.; Wilson, A. J.; Jain, P. K. Ammonia
Oxidation Enhanced by Photopotential Generated by Plasmonic
Excitation of a Bimetallic Electrocatalyst. Angew. Chem., Int. Ed. 2020,
59, 18430−18434.
(23) Prieto, G.; Tu
ysuz, H.; Duyckaerts, N.; Knossalla, J.; Wang, G.-
̈ ̈
H.; Schuth, F. Hollow Nano- and Microstructures as Catalysts. Chem.
̈
Rev. 2016, 116, 14056−14119.
(24) Abu Sohel, S. M.; Liu, R.-S. Carbocyclisation of Alkynes with
External Nucleophiles Catalysed by Gold, Platinum and Other
Electrophilic Metals. Chem. Soc. Rev. 2009, 38, 2269−2281.
(25) (a) Rao, V. G.; Aslam, U.; Linic, S. Chemical Requirement for
Extracting Energetic Charge Carriers from Plasmonic Metal Nano-
particles to Perform Electron-Transfer Reactions. J. Am. Chem. Soc.
2019, 141, 643−647. (b) Aslam, U.; Chavez, S.; Linic, S. Controlling
Energy Flow in Multimetallic Nanostructures for Plasmonic Catalysis.
Nat. Nanotechnol. 2017, 12, 1000−1005. (c) Kale, M. J.; Christopher,
P. Plasmons at the Interface. Science 2015, 349, 587−588.
(26) (a) Manjavacas, A.; Liu, J. G.; Kulkarni, V.; Nordlander, P.
Plasmon-Induced Hot Carriers in Metallic Nanoparticles. ACS Nano
2014, 8, 7630−7638. (b) Guo, J.; Zhang, Y.; Shi, L.; Zhu, Y.;
Mideksa, M. F.; Hou, K.; Zhao, W.; Wang, D.; Zhao, M.; Zhang, X.;
Lv, J.; Zhang, J.; Wang, X.; Tang, Z. Boosting Hot Electrons in
Hetero-Superstructures for Plasmon-Enhanced Catalysis. J. Am. Chem.
Soc. 2017, 139 (49), 17964−17972.
10589
https://doi.org/10.1021/jacs.1c05753
J. Am. Chem. Soc. 2021, 143, 10582−10589