Plasmon Coupling-Induced Hot Electrons for Photocatalytic Hydrogen Generation

Article abstract of DOI:10.1002/asia.202100856

We present the fabrication of core-shell-satellite Au@SiO₂-Pt nanostructures and demonstrate that LSPR excitation of the core Au nanoparticle can induce plasmon coupling effect to initiate photocatalytic hydrogen generation from decomposition of formic acid. Further studies suggest that the plasmon coupling effect induces a strong local electric field between the Au core and Pt nanoparticles on the SiO₂ shell, which enables creation of hot electrons on the non-plasmonic-active Pt nanoparticles to participate hydrogen evolution reaction on the Pt surface. In addition, small SiO₂ shell thickness is required in order to obtain a strong plamon coupling effect and achieve efficient photocatalytic activities for hydrogen generation.

Full text of DOI:10.1002/asia.202100856

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Plasmon Coupling Induced Hot Electrons for Photocatalytic
Hydrogen Generation
Authors: Can Xue, Xu Yuan, Wenlong Zhen, and Sijia Yu
This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.202100856
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A Journal of
A sister journal of Angewandte Chemie
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Chemistry - An Asian Journal
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FULL PAPER
Plasmon Coupling Induced Hot Electrons for Photocatalytic
Hydrogen Generation
[
a]
[a]
[a]
*[a]
Xu Yuan, Wenlong Zhen, Sijia Yu, and Can Xue
[
a]
X. Yuan, Dr. W. Zhen, Dr. S. Yu, Prof. Dr. C. Xue
School of Materials Science and Engineering
Nanyang Technological University
5
0 Nanyang Avenue, 639798, Singapore
E-mail: cxue@ntu.edu.sg
Abstract: We present the fabrication of core-shell-satellite Au@SiO
2
-
stronger local electric field,[14] though the mechanism behind this
mutual effect is still elusive. To verify the hypothesis, a
significantly enhanced local electric field is needed, which may be
Pt nanostructures and demonstrate that LSPR excitation the core Au
nanoparticle can induce plasmon coupling effect to initiate
photocatalytic hydrogen generation from decomposition of formic acid. realized by placing two plasmonic NPs in proximity. Plasmon
Further studies suggest that the plasmon coupling effect induces
strong local electric field between the Au core and Pt nanoparticles on
coupling occurs when plasmon oscillation of the two NPs interacts
with each other.[15] Indeed, the plasmon coupling effect does not
require both metal NPs being capable of LSPR excitation by the
incident light.[16] It means that a plasmon coupled structure with
only one component having LSPR absorption can possibly create
hot electrons on the non-plasmonic-active component, where the
catalytic reaction could be initialized through plasmon coupling
under light excitation.
the SiO
plasmonic-active Pt nanoparticles to participate hydrogen evolution
reaction on the Pt surface. In addition, small SiO shell thickness is
2
shell, which enables creation of hot electrons on the non-
2
required in order to obtain strong plamon coupling effect and achieve
efficient photocatalytic activities for hydrogen generation.
Herein, in order to verify this hypothesis, we have fabricated
core-shell-satellite Au@SiO
hydrogen evolution in formic acid for proof-of-concept. We have
found that the Au@SiO -Pt nanostructure exhibits significantly
enhanced photocatalytic activities as compared with the control
samples without either Au cores or decorated Pt nanoparticles on
2
-Pt nanostructures for photocatalytic
Introduction
2
The electron cloud of noble metal nanoparticles (NPs) oscillates
coherently upon illumination of incident light, this phenomenon is
known as localized surface plasmon resonance (LSPR).[ This
unique process allows plasmonic nanostructures to harvest the
energy of light and convert it into heat and energetic charge
carriers. Therefore, noble metal NPs have been widely used in a
1]
the SiO
2
shell. Further studies suggest that the promoted
-Pt is owing to the Pt hot
photocatalytic activities of Au@SiO
2
electrons that are inductively created from plasmon coupling
between the Au core and Pt nanoparticles on the silica shell.
Moreover, the silica shell thickness plays a crucial role for
plasmon coupling, and significantly influences the photocatalytic
wide range of fields, including bio-imaging,[ cancer therapy,
2]
[3]
drug delivery,[4] optical device,[5] and catalysis.[6] Among these
applications, photocatalysis utilizing the LSPR of plasmonic metal
materials can be a promising solution for efficiently utilizing solar
energy. To figure out the contribution of LSPR to photocatalytic
reactions, some dominant mechanisms have been proposed,
2
activities of the core-shell-satellite Au@SiO -Pt nanostructures.
Results and Discussion
including photothermal effect,[ excitation of hot electrons, and
enhanced local electric field.[9] However, the synergistic effect
between these mechanisms remains elusive.
7]
[8]
2
To obtain the core-shell-satellite Au@SiO -Pt nanostructure, Au
NPs were firstly synthesized. TEM examinations (Figure 1a)
revealed that the average diameter of the as-prepared Au
nanoparticles was 67.65.7 nm. Subsequently, silica-coating was
applied to the Au NPs. By using 0.1 mM TEOS in the sol-gel
Researchers have revealed that LSPR excitation can induce
several non-mutually exclusive processes to assist the
photocatalytic reactions. First, heat is generated when plasmonic
nanostructures absorb light, which results in increasing local
temperature and accelerates reaction rates.[10] Note that the size
of NPs can affect the photothermal efficiency, and the optimum
size is about 40~60 nm.[7b] Second, the enhanced electric field
confined on the metal surface, resulting from electronic oscillation
upon illumination, increases the available amount of photons, and
consequently promote proximal photochemical reactions.[ Third,
hot electrons, arising from non-radiative decay of localized
surface plasmon excitation, could transfer to the adsorbate
molecules or contacted particles to facilitate the related
process, the obtained SiO
2
shell thickness is around 3 nm (Figure
1b). When the TEOS concentration increased to 0.3 mM and 1
2
mM, the SiO shell thickness changed to 10 nm and 18 nm,
respectively (Figure 1c, d).
Finally, Pt NPs with the size of 2~3 nm (Figure 2) were
deposited onto the surface of silica-coated Au (Au@SiO
The composition of the Au@SiO -Pt nanostructure was verified
by EDX mapping (Figure 3). The in-situ decoration of Pt NPs on
the SiO shell could be ascribed to the SPR excitation of the Au
core and the consequent high temperature localized on the SiO
surface to initiate reduction of K PtCl by isopropanol. The
2
) NPs.
11]
2
2
2
[
7a, 8a]
reactions.
2
4
Hot electrons play critical roles in catalytic reactions, but have
problems of limited amount of high-energy electrons[12] and short
lifetime.[13] Previous studies have suggested that amount of hot
electrons increases significantly in proximity to the places with
quantitative elemental composition was identified by inductive
coupled plasma optical emission spectrometry (ICP-OES) with
the Au to Pt atomic ratio as 25.08:1.
1
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Chemistry - An Asian Journal
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between Au and Ag also led to comparable redshift of the two
dimer resonances.[18]
2
For the presented Au@SiO -Pt nanostructures with 3 nm
silica shell thickness, the LSPR peak shifted dramatically from
5
43nm to 686 nm, which is a strong evidence of intense plasmon
coupling between the Au and Pt nanoparticles.[
15c,
17-18]
The
-Pt
shoulder peak at ~540 nm might be due to the Au@SiO
2
particles with very low surface density of Pt nanoparticles.
Because the 3 nm silica shell is too thin to be condensed, on some
Au@SiO nanoparticles, the surface adsorption of [PtCl
2 4
]2- ions
might be fairly weak, which resulted in low photodeposition
density of Pt. Consequently, the influence of plasmon coupling on
the core Au nanoparticle becomes very weak with almost no
spectral shift.
For
nanostructures (3 nm SiO
photocatalyst for visible-light-driven hydrogen generation in the
formic acid solution. As shown in Figure 5, the Au@SiO -Pt
sample presented steady evolution under visible light
irradiation, while the control samples, the Au NPs, Au@SiO NPs,
and Pt decorated SiO (SiO -Pt) NPs showed no activities (Figure
S1). In a further control experiment, the Au@SiO -Pt sample was
placed in formic acid in dark at 70°C, and no H evolution was
a
proof-of-concept application, the Au@SiO
2
-Pt
2
shell thickness) were used as the
2
H
2
2
2
2
2
2
Figure 1. TEM images of (a) Au NPs and Au@SiO NPs with silica shell
thickness of (b) 3nm, (c) 10nm, and (d) 18nm.
2
observed, which allowed us to exclude the photothermal effect
from LSPR excitation of Au.
2 2
Figure 2. TEM images of Au@SiO -Pt (3 nm SiO shell thickness).
The UV-vis analyses showed dramatic change upon Pt
nanoparticle decoration. As shown in Figure 4, the normalized
UV-vis spectrum of Au@SiO NPs presented a sharp LSPR peak
2
at 543 nm. After photodeposition of Pt, the LSPR peak redshifts
drastically to 686 nm, which can be attributed to the plasmon
coupling between the Au core and Pt NPs on the SiO shell.
2
2
Figure 3. EDX mapping of Au@SiO -Pt to show the distribution of the elements
Au, Si and Pt.
When two metal nanoparticles are placed in proximity,
plasmon coupling is established through strong interaction
between their plasmon oscillations. This plasmon coupling
modulates the LSPR frequency of the plasmon coupling
nanostructures. Generally, a favorable coupling of the plasmon
resonance of the coupled nanoparticles requires lower frequency
to drive the coupled plasmon resonance, which leads to redshift
of plasmon band.[15c] Previous researchers have demonstrated
that the redshift of the LSPR peak is strong evidence for plasmon
coupling. For example, the plasmon coupling between 88 nm gold
nanodisc pair with 2 nm interparticle distance (polarized along
interparticle axis) led to a redshift of ~84 nm to 645 nm as
compared to the plasmon band of isolated gold nanodisc, which
was only 561 nm.[17] When individual Au-Ag@SiO
was polarized parallel to dimer axis, the plasmon coupling
heterodimer
2
2 2
Figure 4. UV-Vis Spectra of Au@SiO and Au@SiO -Pt nanoparticles.
2
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These results suggest that the H
surface of Pt NPs which are inactive to visible light. The Au core
is responsible to harvesting the visible light, but LSPR excitation
of individual Au NPs could not initiate the H evolution reaction.
2
Although hot electrons could be generated on Au upon LSPR
excitation, these electrons could not transport through the
2
evolution occurred on the
Since the plasmon coupling effect is critical dependent on the
interparticle distance as the intensity of local electric field decays
with distance r away from the particle as 1/r , the silica shell
thickness in this work becomes an important factor to manage the
local electric field between the Au core and surface Pt NPs. By
varying the TEOS concentration in the silica coating procedures,
3
[19]
insulating SiO
2
shell to Pt NPs for chemical reactions. The only
2
we could obtain different SiO shell thickness including 3 nm, 10
source for hot electrons generation was Pt NPs. As such, we
could hypothesize that the visible light irradiation induces
nm and 18nm. Then the same protocol of Pt photodeposition was
applied for decoration of Pt NPs onto the silica shell. The same
amount of Pt precursor was used for these three samples. Figure
plasmon coupling between the Au core and Pt NPs on SiO
and creates strong local electric field that enables generation of
hot electrons on the Pt NPs to initiate H evolution reaction. The
2
shell
2
8 shows the Au@SiO -Pt samples with the silica shell thickness
2
of 10 nm and 18 nm.
proposed reaction mechanism is depicted in Figure 6.
2
Figure 7. Photocatalytic hydrogen evolution over Au@SiO -Pt under incident
Figure 5. Photocatalytic hydrogen evolution amount over different samples.
light with different wavelength.
In the proposed model, the plasmon coupling involves both
plasmonic Au NP and non-plasmonic Pt NP. The hot electrons
generated on Pt still originate from the LSPR excitation of the
plasmonic Au NP. In order to further verify the contribution from
LSPR excitation of Au, we compared the photocatalytic activities
of the Au@SiO -Pt (3 nm SiO shell thickness) under irradiation
2 2
of two different wavelengths, 430±10 nm and 600±10 nm, with the
same light intensity. As shown in Figure 7, the stronger plasmonic
2
excitation at 600±10 nm results in much higher H evolution rate
than weak excitation at 430±10 nm in spite of higher photon
energy of 430 nm light. This clearly support that the stronger
LSPR excitation allows for more effective generation of hot
electrons on Pt towards higher photocatalytic activities.
Figure 8. TEM images of Au@SiO
2
-Pt with silica shell thickness of (a) 18nm,
(b) 10nm.
Figure 6. Possible photocatalytic reaction mechanism.
2
Figure 9. UV-Vis spectra of Au@SiO -Pt with different silica shell thickness
3
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The UV-vis spectra (Figure 9) show relatively minor shift
upon Pt NP decoration for the samples with 10 nm and 18 nm
shell thickness, suggesting weak plasmonic coupling in these two
Au@SiO
2
-Pt samples since the interaction between Au core and
Pt nanoparticles decreased with enlarged distance.[
15c, 17, 20]
The
visible light photocatalytic test showed more than 9 times lower
evolution activities for these two samples as compared to the
Au@SiO -Pt with 3 nm shell thickness. Note that without silica
shell (0 nm shell thickness), the resulted Au@Pt nanoparticles
Figure S2) showed no photocatalytic activity because the directly
H
2
2
(
attached Pt on Au strong damping of Au LSPR. The FDTD
simulation results, as shown in Figure S3, also indicate larger
redshift of the LSPR band as the silica shell thickness decreases,
which is consistent with the experimental observations.
The above results suggest that at increasing Au-Pt
interparticle distance, the plasmon coupling effect becomes very
weak, and the intensity of local electric field between Au core and
Pt nanoparticles decreases dramatically. Govorov et al. have
previously demonstrated that intensity of plasmonic field directly
correlated with the generation rate of hot electrons.[21] In particular
for plasmon coupling system, the strongly enhanced local electric
field in the gap region allows for drastically increased rate of hot
electron generation on the involved nanoparticle surfaces.[
Therefore in our studies, increased silica shell thickness resulted
in weaker plasmon coupling and consequently lower intensity of
local field. The FDTD simulation results (Figure S4) reveal that for
22]
the Au@SiO
field is present on both Au and Pt particles in the gap region. While
for the Au@SiO -Pt with 10 nm and 18 nm shell thickness, the
2
-Pt with 3 nm shell thickness, strong local electric
2
local electric field on Pt becomes much weaker, which led to
reduced capability of hot electrons on Pt and thus decreased
photocatalytic activities. From this point of view, our observation
suggests that small interparticle distance is ultimately important to
achieve strong Au-Pt plasmon coupling and intense local electric
field for hot electron generation on the non-plasmonic Pt
nanoparticles.
Figure 10. (a) Photocatalytic hydrogen evolution amount over the Au@SiO
samples with different silica shell thickness versus visible light irradiation time;
b) The average H evolution rate over 3 hours for the samples. The Au@SiO
Pt-3nm sample showed an H evolution amount of 45.7umol/mg[Pt] in 3 hours,
which is much higher than Au@SiO -Pt-10nm (5.3umol/mg[Pt]), Au@SiO -Pt-
8nm (2.9umol/mg[Pt]) and Au@Pt (0umol/mg[Pt]). As for Au@Pt, noted that Pt
2
-Pt
(
2
2
-
2
2
2
1
nanoparticles were directly deposited onto Au nanoparticles without silica
coating (Figure S2).
Conclusion
Experimental Section
2
In conclusion, we have synthesized Au@SiO -Pt core-shell-
satellite nanostructures and used this model structure to
demonstrate that plasmon coupling between the Au core and the
Materials
2
Pt NPs on the silica shell could initiate H evolution reaction in
Gold(III) chloride hydrate (HAuCl
citrate (NaCi, 99%), ethanol (99%), tetraethyl orthosilicate (TEOS,
8%), 16-mercaptohexadecanoic acid (MHA, 90%),
hexachloroplatinic (IV) acid hexahydrate (H PtCl ∙6H O)
Potassium tetrachloroplatinate(II) (K PtCl , 98%), 3-aminopropyl-
triethoxysilane (APTES, 99%), ammonium hydroxide solution (30-
3% NH in H O), sodium dodecyl sulfate (SDS, ൒99.0%), formic
acid(( ൒ 96%) and hydrochloric acid fuming (37%) were all
purchased from Sigma-Aldrich. Isopropyl alcohol (൒99.8%) was
purchased from Fisher Chemical. Tetraisopropyl orthosilicate
4
, ൒49.0%, Au Basis), tri-sodium
formic acid solution. Further analyses suggest that the Au-Pt
plasmon coupling may create strong local electric field that
enables hot electron generation on Pt NPs to participate the
9
2
6
2
decomposition of formic acid towards H
importance because it presents
2
evolution. This work is of
new route to initiate
2
4
a
photocatalytic reactions on non-plasmonic nanoparticles by
creating hot electrons through plasmon coupling effect.
3
3
2
(>99.0%) was purchased from TCI. Nitric acid ( ≥ 96%) was
purchased from Honeywell Fluka. All glassware were washed
with aqua regia, HCl: HNO3=3:1(v:v), and rinsed with ethanol and
Milli-Q water. Deionized water (18.2 kΩꞏcm, Milli-Q System,
Millipore, Billerica) was used in all the experiments. All the
chemical reagents were used as received without further
purification.
4
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Characterizations
given period using gas chromatography (Aglient 7890A, TCD, 13
X columns, Ar carrier) and gas chromatography (Shimadzu 2010)
equipped with FID and TCD detectors.
TEM examinations were carried out on
a JEOL 2100F
transmission electron microscope operated at 200kV. UV–vis
absorption spectra were recorded on Shimadzu UV-1800 UV-Vis
spectrophotometer. The gold and platinum content were
measured by inductive coupled plasma on an iCAP6200DUO
ICP-OES spectrometer (Thermo Fisher Scientific).
More experimental details, including synthetic methods,
numerical simulation and characterizations are presented in the
Supporting Information.
Sample preparation
Acknowledgements
Synthesis of gold nanoparticles. The gold nanoparticles were
synthesized using a seed-mediated method. The gold seeds were
prepared by injecting 5 mL NaCi solution (38.8 mM) into 50 mL
boiling HAuCl solution (1 mM) under vigorous stirring. The
4
reaction was kept boiling for 15 min and then cooled to room
temperature for later use as the seeds.
This work is supported by the Ministry of Education, Singapore,
under AcRF-Tier2 (MOE2018-T2-1-017) and AcRF-Tier1
(MOE2019-T1-002-012, RG102/19). The authors also thank the
support from NTU seed funding for Solar Fuels Laboratory.
Keywords: plasmon coupling • hot electrons • photocatalytic
4
Next, 3 mL HAuCl solution (50mM) were added into 247 mL
hydrogen generation • energy transfer
water in a 500mL round bottom flask. Then 2.25 mL as-prepared
Au seeds solution and 5 mL NaCi solution (38.8 mM) were
injected into the flask in sequence after the mixture was boiling.
After 30 min, 10 mL NaCi solution (38.8 mM) was added into the
flask as stabilizer. Then the mixture was kept boiling for 1 hour.
After the reaction completed, the products were separated via
centrifugation, and re-suspended in 0.3 mM NaCi solution.
[1]
a) E. Hutter, J. H. Fendler, Advanced materials 2004, 16,
685-1706; b) K. L. Kelly, E. Coronado, L. L. Zhao, G.
1
C. Schatz, ACS Publications, 2003; c) K. L. Kelly, E.
Coronado, L. L. Zhao, G. C. Schatz, Journal of Physical
Chemistry B 2003, 107, 668-677.
Silica coating of Au nanoparticles. Silica coating was
conducted through a modified Stöber method. Typically, 0.25 mL
ethanol solution of MHA (10mM) was added into 2.5 mL as-
prepared solution of Au nanoparticles in a 20-mL glass vial. After
[2]
a) B. P. Timko, T. Dvir, D. S. Kohane, Advanced
materials 2010, 22, 4925-4943; b) E. Boisselier, D.
Astruc, Chemical society reviews 2009, 38, 1759-1782.
a) S. D. Brown, P. Nativo, J.-A. Smith, D. Stirling, P. R.
Edwards, B. Venugopal, D. J. Flint, J. A. Plumb, D.
Graham, N. J. Wheate, Journal of the American
Chemical Society 2010, 132, 4678-4684; b) P.
Cherukuri, E. S. Glazer, S. A. Curley, Advanced drug
delivery reviews 2010, 62, 339-345.
[3]
30 min, 10 mL TEOS solution (0.1275 mM in IPA) was added to
vial under vigorous stirring. After 15 min, 0.25 mL NH ꞏH O was
3
2
added to the mixture. After 2 hours, 0.1 mL tetraisopropyl
orthosilicate solution (13 mM in IPA) was added to the mixture
[4]
[5]
[6]
A. S. Urban, T. Pfeiffer, M. Fedoruk, A. A. Lutich, J.
Feldmann, ACS nano 2011, 5, 3585-3590.
L. Eurenius, C. Hägglund, E. Olsson, B. Kasemo, D.
Chakarov, Nature Photonics 2008, 2, 360.
a) S.-W. Cao, Z. Yin, J. Barber, F. Y. Boey, S. C. J. Loo,
C. Xue, ACS applied materials & interfaces 2011, 4,
slowly. After
centrifugation and washed with IPA and re-suspended in DI water.
For the Au@SiO nanoparticles with different silica shell thickness
3 nm, 10 nm and 18nm), the concentration of TEOS in the
mixture was tuned to 0.1 mM, 0.3 mM and 1 mM, respectively.
3 hours, the products were collected via
2
(
4
18-423; b) Z. Zhang, Z. Wang, S.-W. Cao, C. Xue, The
Journal of Physical Chemistry C 2013, 117, 25939-
5947; c) W. Zhen, X. Yuan, X. Shi, C. Xue, Chemistry–
Photodeposition of Pt NPs onto Au@SiO
Typically, 6.5 mL solution of as-prepared Au@SiO
was mixed with 13.5 mL IPA and 0.2 mL K PtCl (10 mM) in a 35-
2
nanostructures.
2
2
nanoparticles
An Asian Journal 2020, 15, 2480-2486; d) W. Zhen, J.
Sun, X. Ning, X. Shi, C. Xue, Applied Catalysis B:
Environmental 2021, 120568.
a) G. Baffou, R. Quidant, Chemical Society Reviews
2014, 43, 3898-3907; b) G. Baffou, H. Rigneault,
Physical Review B 2011, 84, 035415; c) A. Gaiduk, P. V.
Ruijgrok, M. Yorulmaz, M. Orrit, Chemical Science 2010,
2
4
mL quartz vial. A 300-W Xenon lamp was used as the light source.
2
The quartz vial was irradiated by full range light (240 mW/cm ) for
[
[
7]
8]
2
hours under mild stirring before the products were collected via
centrifugation.
1
, 343-350.
Measurement of photocatalytic activities
a) M. J. Kale, T. Avanesian, P. Christopher, Acs
Catalysis 2013, 4, 116-128; b) S. Sarina, H. Y. Zhu, Q.
Xiao, E. Jaatinen, J. Jia, Y. Huang, Z. Zheng, H. Wu,
Angewandte Chemie International Edition 2014, 53,
2
The photocatalytic activities of H generation from decomposition
of formic acid in solution were evaluated by using aforementioned
samples as photocatalysts. Typically, 2.2mg as-prepared
samples were dispersed into 10 mL DI water containing 100μL of
formic acid solution (98%). A 20-mL sealed glass vial was used
as reactor and purged with Argon for 15 min to remove residual
air. A 300 W Xenon lamp (MAX-302, Asahi Spectra Company,
Ltd.) coupled with a 420-nm cutoff filter was used as the visible
light source. The solution temperature was maintained as the
same as ambient condition (~25°C). Reaction kinetics were
monitored via analyses of the withdrawn gaseous samples at a
2935-2940; c) M. L. Brongersma, N. J. Halas, P.
Nordlander, Nature nanotechnology 2015, 10, 25-34; d)
J. Li, S. K. Cushing, P. Zheng, T. Senty, F. Meng, A. D.
Bristow, A. Manivannan, N. Wu, Journal of the American
Chemical Society 2014, 136, 8438-8449.
a) Y. Yang, J. Liu, Z.-W. Fu, D. Qin, Journal of the
American Chemical Society 2014, 136, 8153-8156; b) Y.
Tsuboi, R. Shimizu, T. Shoji, N. Kitamura, Journal of the
American Chemical Society 2009, 131, 12623-12627.
N. J. Hogan, A. S. Urban, C. Ayala-Orozco, A. Pimpinelli,
[9]
[10]
5
This article is protected by copyright. All rights reserved.

Chemistry - An Asian Journal
10.1002/asia.202100856
FULL PAPER
P. Nordlander, N. J. Halas, Nano letters 2014, 14, 4640-
645.
4
[
11]
12]
a) U. Aslam, V. G. Rao, S. Chavez, S. Linic, Nature
Catalysis 2018, 1, 656-665; b) X.-C. Ma, Y. Dai, L. Yu,
B.-B. Huang, Light: Science & Applications 2016, 5,
e16017-e16017.
R. Sundararaman, P. Narang, A. S. Jermyn, W. A.
Goddard III, H. A. Atwater, Nature communications 2014,
[
5
, 5788.
[
13]
14]
Y. Zhang, S. He, W. Guo, Y. Hu, J. Huang, J. R. Mulcahy,
W. D. Wei, Chemical reviews 2017, 118, 2927-2954.
H. Harutyunyan, A. B. Martinson, D. Rosenmann, L. K.
Khorashad, L. V. Besteiro, A. O. Govorov, G. P.
Wiederrecht, Nature nanotechnology 2015, 10, 770.
a) E. Hao, G. C. Schatz, The Journal of chemical
physics 2004, 120, 357-366; b) W. Rechberger, A.
Hohenau, A. Leitner, J. Krenn, B. Lamprecht, F.
Aussenegg, Optics communications 2003, 220, 137-
[
[15]
141; c) P. K. Jain, M. A. El-Sayed, Chemical Physics
Letters 2010, 487, 153-164.
[16]
T. Tumkur, X. Yang, C. Zhang, J. Yang, Y. Zhang, G. V.
Naik, P. Nordlander, N. J. Halas, Nano letters 2018, 18,
2
040-2046.
P. K. Jain, W. Huang, M. A. El-Sayed, Nano Letters 2007,
, 2080-2088.
A. Lombardi, M. P. Grzelczak, A. Crut, P. Maioli, I.
Pastoriza-Santos, L. M. Liz-Marzan, N. Del Fatti, F.
Vallée, ACS nano 2013, 7, 2522-2531.
[
17]
18]
7
[
[19]
a) P. K. Jain, S. Eustis, M. A. El-Sayed, The Journal of
Physical Chemistry B 2006, 110, 18243-18253; b) D.
Griffiths, Introduction to Electrodynamics Prentice-Hall,
Upper Saddle River, NJ, 1999.
[20]
[21]
[22]
K.-H. Su, Q.-H. Wei, X. Zhang, J. Mock, D. R. Smith, S.
Schultz, Nano letters 2003, 3, 1087-1090.
H. Zhang, A. O. Govorov, The Journal of Physical
Chemistry C 2014, 118, 7606-7614.
L. V. Besteiro, X.-T. Kong, Z. Wang, G. Hartland, A. O.
Govorov, Acs Photonics 2017, 4, 2759-2781.
6
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Chemistry - An Asian Journal
10.1002/asia.202100856
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2
The Au@SiO -Pt core-shell-satellite structure was synthesized, and used to demonstrate that hot electrons generated on Pt
nanoparticles induced by plasmon coupling between the Au core and the Pt NPs on the silica shell could initiate H
in formic acid solution.
2
evolution reaction
7
This article is protected by copyright. All rights reserved.