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Multi-Layered PtAu Nanoframes and Their Light-Enhanced

Electrocatalytic Activity via Plasmonic Hot Spots
Soohyun Lee, Jaewon Lee, Sungwoo Lee, MohammadNavid Haddadnezhad,
Myeong Jin Oh, Qiang Zhao, Sungjae Yoo, Lichun Liu, Insub Jung,* and Sungho Park*

1. Introduction
Here, the rational design of complex PtAu double nanoframes (DNFs) for
plasmon-enhanced electrocatalytic activity toward the methanol oxidation Designing structurally complex nanocrys-
reaction (MOR) is reported. The synthetic strategy for the DNFs consists tals by engineering the atomic arrange-
of on-demand multiple synthetic chemical toolkits, including well-faceted ment of exposed atoms is important
not only for the elucidation of physico-
Au growth, rim-on selective Pt deposition, and selective Au etching steps.
chemical properties at the nanoscale but
DNFs are synthesized by utilizing Au truncated octahedrons (TOh) as a also for the development of cost-effective,
starting template. The outer octahedral (Oh) nanoframes (NFs) nest the inner highly efficient nanocatalysts for a variety
TOh NFs, eventually forming DNFs with a tunable intra-nanogap distance. of applications including CO2 reduction,
Residual Au adatoms on Pt skeletons act as light entrappers and produce the methanol oxidation reaction (MOR),
the hydrogen evolution reaction (HER),
plasmonic hot spots between inner and outer frames through localized
and the oxygen reduction reaction (ORR).
surface plasmon resonance (LSPR) coupling, which promotes enhanced Specifically, nanoframes (NFs) have been
electrocatalytic activity for the MOR. Importantly, the correlation between the considered as a next-generation can-
gap-induced hot carriers and electrocatalytic activity is evaluated. The highest didate for nanocatalysts because their
catalytic activity is achieved when the gap is the narrowest. To further harness open structures allow for a high ratio of
their light-trapping capability, hierarchically structured triple NFs (TNFs) are catalytic active surfaces per given mass,[1]
which leads to outstanding catalytic per-
synthesized, wherein three NFs are entangled in a single entity with a high
formances compared to analogous solid
density of hot regions, exhibiting superior electrocatalytic activity toward the nanoparticles (NPs).[2] For example, Chen
MOR with a sixfold larger current density under light irradiation compared to et al. reported PtNi bimetallic NFs with
the dark conditions. a higher ORR activity than Pt/C catalysts
due to the increased volume of the con-
fined space within the NF structures,
demonstrating the importance of the rational design of NF
structures for electrocatalysis.[3] However, the structural archi-
S. Lee, J. Lee, S. Lee, M. Haddadnezhad, M. J. Oh, Q. Zhao, S. Yoo,
tecture of recent catalytic NFs is limited to single rim-based
I. Jung, S. Park NFs resembling or molded from platonic nanocrystals. The
Department of Chemistry further introduction of additional building complexities inside
Sungkyunkwan University frames (e.g., multiple frame layers) would lead to a higher
Suwon 16419, Republic of Korea electrochemical active surface area, with additional advantages
E-mail: [email protected]; [email protected]
via light energy conversion to hot carriers (electrons or holes)
S. Yoo
Research Institute for Nano Bio Convergence (vide infra).
Sungkyunkwan University On the other hand, great efforts have been made to employ
Suwon 16419, Republic of Korea bimetallic components such as plasmonic and catalytic metals[4]
L. Liu because localized surface plasmon resonance (LSPR), a col-
College of Biological lective oscillation of free electrons at the surface of plasmonic
Chemical Sciences and Engineering & Nanotechnology Research
Institute
metal NPs such as Au and Ag, can significantly promote the
Jiaxing University generation of hot carriers and consequently enhance electrocat-
Jiaxing 314000, P. R. China alytic reactions. For example, Wang et al. reported that Au@Pt
S. Lee, I. Jung NPs can generate hot holes to boost the electrocatalytic activity
Institute of Basic Science of transition metals toward ammonia oxidation reactions and
Sungkyunkwan University Zheng et al. demonstrated enhanced hydrogen generation ena-
Suwon 16419, Republic of Korea
bled by the generation of energetic hot electrons via a highly
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202206377.
concentrated electromagnetic field at the tips of Pt-modified
Au nanorods.[5] However, how plasmon-enhanced electrocata-
DOI: 10.1002/smll.202206377 lysts are correlated with plasmonic excitation at the nanogaps is

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largely unknown because there is a lack of synthetic principles one can design complex multi-NFs for highly efficient plasmon-
for the realization of such nanostructures that simultaneously enhanced electrocatalysis.
possess tunable intra-particle gaps and bimetallic components
for plasmon-assisted electrocatalytic applications.
Herein, we demonstrate that the synthetic method of multi- 2. Results and Discussion
layered PtAu double NFs (DNFs) for light-enhanced electro-
catalysis was significantly improved by plasmonic hot spots 2.1. Synthesis of TOh@Oh PtAu Double Nanoframes (DNFs)
produced at the nanogaps among multiple frames in a single
entity. PtAu DNFs obtained through multiple chemical tool- Scheme 1 shows a schematic illustration of the synthetic
kits are composed of inner truncated octahedral (TOh) NFs pathway of truncated-octahedral@octahedral (TOh@Oh) PtAu
and outer octahedral (Oh) NFs with tunable intra-nanogap dis- DNFs where inner TOh NFs and outer Oh NFs are connected
tances between the frames. Owing to the plasmonically active through thin metal ligaments. By using TOh Au NPs as a
Au domain that induces hot carriers under incident light, the starting template, multiple chemical toolkits including 1) selec-
electrocatalytic performance toward the MOR was significantly tive deposition of Pt, 2) well-faceted overgrowth of Au, and 3)
enhanced. Notably, the hot spots generated from intra-particle etching of inner Au are systematically applied, which was modi-
plasmon coupling between two adjacent residual Au domains fied from our previous literature.[6]
in DNFs greatly boosted the electrochemical reaction efficiency. Briefly, to explain, we first applied the selective Pt deposition
The correlation between hot spots with electrocatalytic activity step to TOh Au NPs (Figure S1A, Supporting Information) to
was further verified by precisely tuning the gap distances prepare TOh Au@Pt NPs (Figure S1B, Supporting Informa-
between inner and outer NFs. In addition, by nesting one more tion). Under the Ag+ and reducing agent (ascorbic acid) envi-
NF into DNFs, triple NFs (TNFs) were successfully prepared, ronment, Pt4+ was selectively reduced at the edges of the TOh
exhibiting maximized hot regions for light energy conversion Au NPs (energetically unstable) via a galvanic replacement reac-
to hot carriers. The exemplified synthetic strategy shows how tion between Pt4+ and the pre-formed thin layer of Ag. Then,

Scheme 1. Schematic illustration of the synthetic strategy of TOh@Oh PtAu DNFs with different intragap distances through multiple chemical toolkits
including selective Pt deposition, well-faceted Au overgrowth, and etching of inner Au steps.

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Figure 1. A) FE-SEM and B) HAADF-STEM images of TOh@Oh PtAu DNFs. C) EDS line profile data of the TOh@Oh PtAu DNF along the yellow line
depicted in panel (B). D) HAADF-STEM and EDS mapping images of TOh@Oh PtAu DNF viewed from the <100> direction. The scale bar in panel D
is 50 nm. E) The magnified EDS images of the white dotted box in panel (D) and atomic percentages of Au and Pt in the outer and inner nanoframes.
The scale bar in panel E is 7 nm.

we introduced the well-faceted overgrowth of the Au step where resulting NFs. The energy dispersive spectroscopy (EDS) line
Au grew epitaxially, covering TOh Au@Pt NPs, which eventu- scan in the HAADF-STEM image clearly shows an empty
ally led to the formation of TOh@Oh Au NPs with eight well- space (i.e., gaps) between the inner and outer NFs (Figure 1C).
defined (111) facets (Figure S1C, Supporting Information).[7] The HAADF-STEM image viewed from the <100> direction
After repeating selective Pt coating, Pt was selectively deposited (Figure 1D) shows that the inner TOh NFs are positioned at the
on the edges of the outer Oh Au NPs by a galvanic reaction center and the outer Oh NFs wrap the core TOh in a symmetric
between Ag and Pt4+, forming TOh@Oh Au@Pt NPs (Figure fashion, while maintaining even gap distances (≈18 nm from
S1D, Supporting Information). Last, selective inner Au etching each ridge) within a single entity.
was conducted through a comproportional reaction by Au3+ Figure 1D shows the EDS mapping image of DNFs, which
(AuCl4− + 2Au + 2Cl− → 3AuCl2−), leaving TOh@Oh PtAu are mainly composed of Pt (≈51%), the second major com-
DNFs where the inner and outer frames are connected through ponent Au (≈39%), and Ag (≈10%). Interestingly, the detailed
thin metal ligaments with tunable nanogaps (Figure 1A). Given compositional analysis reveals that the relative atomic composi-
that the Au adatoms remained intact with the neighboring Pt tions of Pt and Au in each inner and outer frame of the TOh@
skeletons even after the Au etching, we hypothesized that the Oh PtAu DNFs (Figure 1E) are different, where the atomic per-
residual Au would act as light absorbers, producing LSPR and, centage of Au is higher in the inner frame (45%) than in the
consequently, gap-induced hot spots, as long as the distances outer frame (34%). It is noteworthy that the inner Pt frames
between the inner and outer frames were close enough, similar are completely covered by Au and the outer Pt frames are in
to commonly investigated nanogaps in spherical Au dimers.[8] half contact with the core Au during the synthesis. Therefore,
after Au etching, the inner Pt frames are covered with a higher
amount of Au and the outer Pt frames are covered with a lower
2.2. Structural and Compositional Characterization of TOh@Oh amount of Au (see Scheme 1). We conducted X-ray photoelec-
PtAu DNFs tron spectroscopy (XPS) analysis of the TOh@Oh PtAu DNFs,
Au NPs (from Au TOh NPs), and Pt NPs (from commercially
Field-emission scanning electron microscopy (FE-SEM) and available Pt black) (Figure S2, Supporting Information). The Au
high-angle annular dark-field-scanning transmission electron 4f spectrum showed binding energies of 87.03 eV (Au 4f5/2) and
microscopy (HAADF-STEM) images of TOh@Oh PtAu DNFs 83.38 eV (Au 4f7/2), and the Pt 4f spectrum reveals binding ener-
with a size of 138 ± 5 nm are shown in Figure 1A,B, clearly gies of 73.78 eV (Pt 4f5/2) and 70.46 eV (Pt 4f7/2). The binding
demonstrating the highly homogeneous size and shape of the energies of both Au and Pt were negatively shifted, as compared

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to those in pure Au (87.38 eV for 4f5/2 and 83.68 eV for 4f7/2) and measurement, respectively). The broad “double-layer” region
Pt NPs (74.38 eV for 4f5/2 and 71.08 eV for 4f7/2), indicating that with commercial Pt/C originates from the carbon and the
Pt and Au existed as an alloy form in PtAu DNFs.[9] In this case, ECSA is 172 cmPt2/mgPt.
Au was directly exposed on the surface and partially embedded Figure 2B–D shows the CV results for the MOR performed
within the matrix of Pt atoms, forming PtAu alloy.[1a] during the electro-oxidation of 0.3 m CH3OH in 0.1 m H2SO4
In addition, we prepared Oh single NFs (SNFs) for the com- under dark and light-irradiated conditions. Laser excitation of
parison of their optical and electrochemical properties with 808 nm with an energy flux of 0.63 W cm−2 was used to gen-
DNFs (see Figure S3, Supporting Information). Figure S4, Sup- erate hot electrons (or hot holes) from the PtAu NFs because
porting Information, shows the UV–vis–NIR extinction spectra both NFs have LSPR extinction features at 808 nm wavelength.
of the TOh@Oh PtAu DNFs, Oh PtAu SNFs, and commercially All current density values were normalized by the ECSA of each
available Pt/C (10 wt%) NPs. As Pt is plasmonically inactive in sample. The current density under dark conditions (dashed
the given spectral window, the Pt/C NPs have no spectral fea- lines in Figure 2B–D) toward the MOR of the Pt/C samples
tures in the vis–NIR region.[10] On the other hand, both TOh@ (0.297 mA cmPt−2) was larger than that of both TOh@Oh PtAu
Oh PtAu DNFs and Oh PtAu SNFs exhibit broad absorption fea- DNFs (0.256 mA cmPt−2) and Oh PtAu SNFs (0.234 mA cmPt−2)
tures covering the visible to NIR region, which originates from during the positive potential sweep. Under laser irradiation, the
the plasmonically active surface Au coating on NFs. The center PtAu NFs exhibited 3.2 (for Oh PtAu SNFs) and 4.3 (for TOh@
of the LSPR band of Oh PtAu SNFs positioned at 1030 nm, which Oh PtAu DNFs) times higher current densities than under
is a similar feature to Oh PtAu SNFs with a thin Au layer.[7] It is dark conditions, whereas the Pt/C samples showed a 1.9 times
noteworthy that TOh@Oh PtAu DNFs show an LSPR band cen- enhancement. Under light irradiation, the current densities of
tered at λmax = 771 nm, similar to the optical profile of the solid the NFs (0.7 mA cmPt−2 for Oh PtAu SNFs and 1.1 mA cmPt−2
TOh@Oh Au@Pt NPs (λmax = 697 nm) (Figure S8, Supporting for TOh@Oh PtAu DNFs) were superior to that of the Pt/C
Information). The existence of a thin Au layer on the NF surface samples (0.5 mA cmPt−2) in the positive sweep direction. The
induces the intra-particle LSPR coupling and eventually con- estimated mass and specific activities of the TOh@Oh PtAu
tributes to the featured appearance of the LSPR band, behaving DNFs measured at 0.6 V showed superior activity among the
as solid Oh Au@Pt NPs. The existence of a trace amount of a samples under the light condition (Figure S5, Supporting Infor-
surface Au coating allows the plasmonically inactive Pt NFs to mation). It should be noted that the observed enhancement for
behave like plasmonically active Au NFs. the Pt/C samples mainly resulted from the photothermal effect
of Pt,[11] given that the measured temperature change was ≈7 °C
(Figure S6, Supporting Information), whereas TOh@Oh PtAu
2.3. Light-Enhanced Electrocatalytic Activity DNFs showed a relatively small temperature change (≈2 °C).
of TOh@Oh PtAu DNFs Therefore, the catalytic performances of the NFs were mostly
boosted by the hot carrier (especially hot hole) generation from
To investigate the electrocatalytic activity of TOh@Oh PtAu the Au domains.
DNFs, we performed cyclic voltammetry (CV) with TOh@Oh To further differentiate the effect of the plasmonic hot spots
PtAu DNFs, Oh PtAu SNFs, and commercial Pt/C (10 wt%). on the catalytic activity, TOh@Oh Pt DNFs were prepared by
Each sample was dispensed on glassy carbon electrodes (GCEs) depositing a thin layer of Pt where the plasmonic nanogaps
with the assistance of Nafion to enhance their adhesion to the were removed (i.e., no exposed Au); thus, eliminating the con-
substrate. In panels A–D, the black, blue, and red traces refer to tribution of hot spots (Figures S7A,B and S7D, Supporting
Pt/C, Oh PtAu SNFs, and TOh@Oh PtAu DNFs, respectively. Information show structural information and EDS mapping
The representative CV curves obtained from −0.2 to 1.6 V at data, respectively). The CV curve provides direct evidence
a scan rate of 50 mV s−1 in a N2 saturated environment with where the oxide reduction peak of Pt (at 0.40 V) is increased
the 0.1 m H2SO4 electrolyte are shown in Figure 2A. The pres- whereas the peak of Au oxide reduction at 0.86 V is suppressed
ence of a symmetric current profile below ≈0 V corresponding after Pt coating (Figure S7E, Supporting Information). The cur-
to “reversible hydrogen adsorption and desorption,” and the rent density of the TOh@Oh Pt DNFs (blue line) during the
anodic formation (above ≈1.5 V) and cathodic removal of oxide MOR shows only a 2.2 times enhancement under light irradia-
at 0.4 V are familiar features of Pt electrochemistry. The blue tion, which is suppressed compared to the 4.2 times enhance-
and red traces are the corresponding voltammograms obtained ment of the TOh@Oh PtAu DNFs, verifying the importance
from Oh PtAu SNFs and TOh@Oh PtAu DNFs, respectively, of hot spots in the light-induced catalytic enhancement with
both showing one additional cathodic feature at 0.9 V, indi- TOh@Oh PtAu DNFs. In addition, TOh@Oh Au@Pt NPs (i.e.,
cating exposure of the Au surface. Their electrochemical surface fully filled with the Au) were also prepared (Figure S7C, Sup-
area (ECSA) was estimated by integrating the HUPD desorption porting Information). The increased oxide reduction Au peak
current–potential profiles below 0 V. As the number of PtAu (at 0.86 V) in the CV curve (black line) verifies the increased
layers increases from one to two in a single entity, the electro- Au domain in the TOh@Oh Au@Pt NPs (Figure S7E, Sup-
catalytic active domain increases, as confirmed by the estimates porting Information) and shows only a 2.5 times light enhance-
of specific ECSAs: 8.95 × 10−2 cmPt2 for TOh@Oh PtAu DNFs ment toward the MOR, again confirming that the presence
and 8.95 × 10−2 cmPt2 for Oh PtAu SNFs (141 cmPt2/mgPt for of nanogaps within TOh@Oh PtAu DNFs is important for
TOh@Oh PtAu DNFs and 48 cmPt2/mgPt for Oh PtAu SNFs, further light-induced catalytic enhancement. Moreover, as
after normalization by the mass obtained from inductively the NFs have multiple thin frames (12 frames for SNFs and
coupled plasma-optical emission spectroscopy (ICP-OES) 36 for DNFs) that are not aligned in one direction, there might

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Figure 2. A) CV curves obtained in a N2-saturated 0.1 m H2SO4 solution. CV curves of B) Pt/C NPs, C) Oh PtAu SNFs, and D) TOh@Oh PtAu DNFs
obtained in a N2-saturated 0.1 m H2SO4 and 0.3 m CH3OH solution under dark (dashed lines) and light (solid lines) conditions. The CV curves in panels
(A,B–D) are normalized by the geometric area of the electrode and the electrochemical surface area of Pt in each experiment, respectively.

be multi-scattering events, which is one of the reasons for the measurements because of the rigid Pt skeletons (Figure S8B,C,
strong light absorption of NFs, which does not occur in solid Supporting Information).
NPs. We conducted chronoamperometric measurements with
TOh@Oh PtAu DNFs and Pt/C (10 wt%) NPs to check electro-
catalytic durability (Figure S8A, Supporting Information). The 2.4. Correlation of the Intra-Nanogap Distance With Light
current density of Pt/C samples decreased rapidly, whereas that Enhancement Toward The Electrocatalytic Activity
of TOh@Oh PtAu DNFs was relatively stable. The high stability of TOh@Oh PtAu DNFs
of DNFs was attributed to the co-existence of Pt and Au, while
pure Pt was easily poisoned by CO molecules during the MOR. It is conventionally recognized in plasmonics that the electro-
In addition, we confirmed that the structures of TOh@Oh magnetic field is strongly enhanced at nanogaps between two
PtAu DNFs retained their shapes without discernible mor- adjacent plasmonic NPs.[12] Thus, to correlate the observed
phological changes before and after the chronoamperometric light-induced catalytic enhancement with the gap distance,

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we measured the electrocatalytic activity of TOh@Oh PtAu demonstrating that the nanogap distance directly correlates
DNFs as a function of the intra-nanogap distance. By control- with the light-induced electrocatalytic enhancement. As the gap
ling the thicknesses of the Au layers during the well-faceted distance becomes short, the mass activities increase exponen-
Au overgrowth step (Scheme 1; Figure S9, Supporting Infor- tially. It is well-known that the magnitude of the electromag-
mation), tunable intra-nanogaps in TOh@Oh PtAu DNFs (i.e., netic field in nanogaps exponentially increases as the distance
the distances between the inner TOh NFs and outer Oh NFs) of nanogaps decreases.[13] The finite-difference time-domain
could be achieved after the inner Au etching step, as shown (FDTD) simulations (Figure S13A–C, Supporting Information)
in Figure 3A–C. Each sample showed a highly homogeneous clearly show that electromagnetic field enhancement of TOh@
shape, size, and double-frame morphology. The measured Oh DNFs was increased as the gap distances became narrower,
average intra-gap distances were 8 ± 2 nm (panel A), 14 ± 5 nm which is in good agreement with our observations. In addi-
(panel B), and 18 ± 6 nm (panel C), as estimated from the his- tion, all of the samples showed a linear increase with the cur-
togram shown in Figure S10, Supporting Information. The rent density at 0.6 V with the laser power ranging from 0.32 to
estimated ECSAs of the gap-controlled DNFs were 143, 146, 1.28 W cm−2 (Figure 3F; Figure S14, Supporting Information),
and 147 cm2 per mgPt for the PtAu DNFs shown in panels indicating that the number of hot electrons varies as a function
Figure 3A–C, respectively (see Figure S11, Supporting Informa- of the laser power as well as the gap distance.
tion for Hupd). The typical CVs measured for these samples are
displayed in Figure 3D, showing a similar current magnitude
for the MOR under dark conditions, indicating that the exposed 2.5. Maximized Light-Induced Enhancement of
Pt surface areas are similar to each other, while the increase C@TOh@Oh PtAu Triple Nanoframes (TNFs)
of current under light varies depending on the gap distance.
For the detailed comparison, we normalized the current into Last, we prepared cube@truncated octahedral@octahedral (C@
the mass activity and plotted the results in Figure 3E. The TOh@Oh) PtAu triple NFs (TNFs) to fully maximize the electro-
exponentially increasing tendency of the peak current density magnetic near-field focusing capability, which was predicted in
(at 0.6 V in the positive potential sweep) is clearly noticeable, the FDTD simulation (Figure S13D, Supporting Information),

Figure 3. A–C) FE-SEM and HR-TEM images of TOh@Oh PtAu DNFs with different intra-nanogap distances. D) CV curves toward the methanol
oxidation reaction under dark (dashed lines) and light (solid lines) conditions. E) Mass activities under dark (dashed boxes) and laser-irradiated (solid
boxes) conditions. F) Peak current densities at 0.6 V versus Ag/AgCl plotted as a function of the laser intensity. The scale bars in the inset HR-TEM
images are 50 nm. The CV curves in panel (D) are normalized by the electrochemical surface area of Pt in each experiment.

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Figure 4. A) FE-SEM, B) HR-TEM, C) HAADF-STEM, and EDS mapping images of C@TOh@Oh PtAu TNFs (the scale bars in TEM images are 50 nm).
D) CV curves toward the MOR under dark (dashed line) and light conditions (solid line). Inset: CV curve obtained in a N2-saturated 0.1 m H2SO4 solu-
tion. E) Specific and mass activities of C@TOh@Oh PtAu TNFs under dark (dashed box) and laser-irradiated (solid box) conditions.

thereby promoting electrocatalytic activity. The C@TOh@ their superior catalytic characteristics (Table S1, Supporting
Oh PtAu TNFs were prepared by repeatedly applying a well- Information).
faceted Au overgrowth step starting from Au nanocubes (Fig- Overall, by fine-tuning the number and nanogap distances
ures S15 and S16, Supporting Information for each chemical of the multiple PtAu NFs, the electrocatalytic performance can
step). The FE-SEM and HR-TEM images of PtAu TNFs shown be further enhanced by gap-induced hot spots in a single entity.
in Figure 4A,B exhibit a well-defined morphology with highly Given that there is a myriad of possible designer hierarchical
homogeneous size and shape. The HR-TEM image viewed multi-NFs for maximizing hot zone densities, the suggested
from the <100> direction clearly shows that three individual synthetic strategies will open up new avenues for light-induced
NFs with different geometries (cubic, truncated octahedral, catalysis.
and octahedral frames) are precisely overlapped and placed
within one entity. From the EDS elemental mapping analysis,
the atomic fractions of Au, Pt, and Ag are 40%, 50%, and 10%, 3. Conclusion
respectively (Figure 4C). The extinction spectrum of PtAu TNFs
shows the LSPR band centered at 661 nm, which is attributed In summary, we report the synthesis of multi-layered NFs
to the stronger plasmonic coupling amongst the interior PtAu consisting of electrocatalytic-active and plasmonic-active com-
NFs (Figure S17, Supporting Information). ponents in a frame fashion with high intricacy and plasmon-
The inset of Figure 4D shows the CV curve of C@TOh@ assisted electrocatalytic activity toward the MOR system. TOh@
Oh PtAu TNFs, indicating the presence of exposed Pt and Au Oh PtAu DNFs were successfully fabricated through multiple
surfaces. The CV profiles clearly reveal a significant increase in synthetic pathways, including well-faceted growth of Au, selec-
light-induced catalytic enhancement based on the comparison tive deposition of Pt, and selective etching of Au. The resulting
between the dashed and solid traces in Figure 4D. The observed PtAu DNFs showed plasmon-enhanced electrocatalytic perfor-
enhancement originates from the additional PtAu NFs that are mance toward the MOR due to the formation of hot spots at
sandwiched between the core and outer NFs, which therefore the narrow nanogaps between the inner TOh NFs and outer
leads to the increased hot spot density as well as the decrease Oh NFs. By precisely controlling the gap distances between
of the gap distance (≈7 nm). There are ≈sixfold increases in the inner and outer rims in a single entity, we showed that the
both the specific and mass activities under the light as com- enhancement of the electrocatalytic activity was mainly attrib-
pared to under the dark conditions (Figure 4E). Schematically, uted to the highly enhanced electromagnetic near-field collec-
the mechanism of plasmon-induced enhancement of MOR per- tion at the nanogaps. Importantly, by successfully synthesizing
formance is proposed based on the previous analysis (see Note TNFs, the density of the hot spots was maximized, resulting
S1 and Figure S18, Supporting Information).[5b] The enhance- in further enhancement of the electrocatalytic activity. This
ment value of C@TOh@Oh PtAu TNFs is much greater than unique frame architecture will shed new light on the design of
other reported light-enhanced MOR nanocatalysts, showing plasmon-enhanced electrocatalysts with high efficiency.

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