PT Decorated Au Nanosphere CuSe Ultrathin Nanoplate Tangential Hybrids For Efficient

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Pt Decorated (Au Nanosphere)/(CuSe Ultrathin Nanoplate)

Tangential Hybrids for Efficient Photocatalytic Hydrogen
Generation via Dual-Plasmon-Induced Strong VIS–NIR
Light Absorption and Interfacial Electric Field Coupling
Liang Ma,* Da-Jie Yang, Xiang-Ping Song, Hai-Xia Li, Si-Jing Ding,* Lun Xiong,
Ping-Li Qin, and Xiang-Bai Chen*
ideal photocatalyst, it should simulta-

The rational regulation of geometry and dimension of plasmonic metal/ neously possess following advantages to
semiconductor photocatalysts is crucial to optimize their photocatalytic achieve high photocatalytic efficiency.
performance by maxing the plasmonic effect. Herein, Au/CuSe/Pt hybrids with a First and foremost, the chosen photocata-
lyst should have strong absorption of the
tangential structure and strong dual-plasmon resonance are prepared, for the
solar light in a broad wavelength region.[4]
first time, through a convenient hydrothermal method, which display a Meanwhile, the photocatalyst should gener-
prominent photocatalytic hydrogen generation activity from water splitting. ate abundant electron–hole pairs, and the
In the ternary nanostructure, a 2D CuSe ultrathin nanoplate is grown along the ability of effective charge separation is
tangent of Au nanospheres, and Pt nanoparticles are deposited on Au and CuSe. highly required.[5,6] In addition, the ade-
Under visible and near-infrared (VIS–NIR) light irradiation, the Au/CuSe/Pt quate superficial areas and active sites for
photocatalytic reaction are necessary.[7,8]
hybrids exhibit an outstanding photocatalytic hydrogen generation activity, that is,
Traditional semiconductors, such as TiO2[9]
7.8 and 9.7 times that of Au/CuSe and Pt/CuSe, respectively. In an Au/CuSe/Pt and ZnO,[10] can produce large amounts of
nanosystem, CuSe and Au are both plasmonic units for light harvesting and photogenerated carriers under ultraviolet
near-field enhancement, and Pt is cocatalyst for hydrogen reaction. Numerical light irradiation; yet, the poor visible light
simulations verify that Au and CuSe have strong electric field coupling around absorption and fast recombination rate of
their interface, which can improve the abilities of light trapping and charge electron–hole pairs immensely limit their
photocatalytic performance. Plasmonic
generation. Moreover, the closely contacted components and tangential archi-
noble metal nanocrystals enabling to harvest
tecture of Au/CuSe/Pt hybrids can generate multiple electron-transfer pathways and concentrate photons by surface plas-
and abundant surface-active sites, which arrestingly enhance the utilization of mon resonance (SPR) are very promising
dual-plasmon-induced hot electrons and photoexcited charges, thus boosting as the key materials for highly efficient
hydrogen generation. photocatalytic hydrogen production.[11–15]
Hetero-photocatalysts composed of noble
metal nanocrystals and semiconductors
have been proved to possess much better
1. Introduction photocatalytic activity than single component.[16–22] In metal/
semiconductor hetero-nanostructures, the SPR excitation
Semiconductor-based photocatalytic hydrogen production from derived strong light absorption ranging from visible to near-
water splitting has been regarded as a promising clean energy infrared region could improve the light-harvesting efficiency.[23]
method for alleviating the increasing energy crisis.[1–3] As an Meanwhile, the strong local electric field of metal nanocrystals
Dr. L. Ma, Dr. H.-X. Li, Prof. L. Xiong, Prof. P.-L. Qin, Prof. X.-B. Chen Prof. S.-J. Ding
Hubei Key Laboratory of Optical Information and Pattern Recognition School of Mathematics and Physics
Wuhan Institute of Technology China University of Geosciences (Wuhan)
Wuhan 430205, P. R. China Wuhan 430074, P. R. China
E-mail: maliang@wit.edu.cn; xbchen@wit.edu.cn E-mail: dingsijing@cug.edu.cn
Dr. D.-J. Yang Dr. X.-P. Song
Beijing Computational Science Research Center Department of Gastrointestinal Surgery
Beijing 100193, P. R. China Xiangya Hospital
Central South University
The ORCID identification number(s) for the author(s) of this article Changsha 410083, P. R. China
can be found under https://doi.org/10.1002/solr.201900376.
DOI: 10.1002/solr.201900376
Sol. RRL 2020, 4, 1900376 1900376 (1 of 9) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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can enhance the bandgap absorption and exciton generation with and CuSe using as cocatalyst. We demonstrated the excellent
the semiconductor.[24] Moreover, the plasmon-induced hot elec- photocatalytic activity of Au/CuSe/Pt tangential hybrids using
trons transfer from metal to semiconductor can noteworthily them for water splitting with visible light (λ > 420 nm) irradia-
accelerate the hydrogen generation reaction.[25] tion. Ternary Au/CuSe/Pt hybrids have been confirmed to show
The 2D semiconductor materials have attracted exponentially the best photocatalytic activity than binary Au/CuSe and Pt/CuSe
increased attention since the discovery of graphene. Compared hybrids. Afterward, the enhanced mechanism for the high
with low-dimensional photocatalysts, 2D semiconductor materi- photocatalytic activity is discussed.
als show better photocatalytic activity due to their unique
thickness-dependent physicochemical features.[26–28] As is
expected, combining of plasmonic metal nanocrystals with 2D 2. Results and Discussion
materials could obviously optimize the abilities of light harvest-
ing and effective charge separation of the hybrids, due to the The growth of CuSe nanoplates along the tangent of Au nano-
strong interaction between the two components at oriented nanospheres was achieved by a convenient hydrothermal method.
scale.[29–33] As a typical and widely studied semiconductor, The detailed synthetic processes are progressively shown in
2D CuSe nanostructures, such as nanoplates and nanosheet, Figure 1a. Pure CuSe nanoplates were synthesized using cupric
show enormous potential for photocatalytic applications due to nitrate as precursor, NaHSe as selenium source, and cetyltrime-
their excellent photoelectric characteristic and near-infrared thylammonium bromide (CTAB) as surface capping agent. The
SPR.[34–40] However, 2D CuSe nanostructures are usually too analogous mechanism of CTAB-assisted growth of CuSe hexa-
thin to trap enough visible light, which inevitably restrict their gonal nanoplates was demonstrated by Zha and co-workers.[36]
performance for light-driven photocatalytic reactions. Recently, With adding as-prepared Au nanospheres into the mixture solu-
Au/Cu2 xSe hybrids have been investigated for biological appli- tion, the CuSe nanoplates could start growing at the surface of Au
cations; in these hybrids, the Cu2 xSe nanocrystals usually exhib- nanospheres, and then enlarging along the tangent of Au nano-
ited unfixed morphology and nonstoichiometric phases.[41–43] sphere. In this process, CTAB solution plays two critical roles:
To date, researches about controlled preparation of plasmonic 1) assisting the growth of CuSe nanoplates and 2) co-operating
metal/2D CuSe hybrids have not been reported so far, due to with Cu2þ and ascorbic acid for the growth of semiconductor
the limit of synthetic strategy. The traditional methods for synthe- on the surface of Au (the mechanism had been discussed in
sizing metal/2D materials catalysts are mainly by depositing our previous work[51]). Figure 1b and Figure S1, Supporting
metal nanocrystals on as-prepared 2D materials or directly mixing Information, show the transmission electron microscopy
the two as-prepared components together.[44–46] In these strate- (TEM) images of CuSe nanoplates, which revealed that CuSe
gies, the structure and morphology of the hybrids, which are nanoplates have irregular morphology and different sizes.
critical factors for plasmon-enhanced photocatalysis, are usually Figure 1c displays that the staring Au nanospheres have an
hard to control. Therefore, more efforts should be paid not only average diameter of 20 nm. To observe the gradual growth of
to synthesize metal/2D materials hybrids, but also to rationally Au/CuSe hybrids, the time-dependent characterization of
regulate the geometry and structure of the hybrids. morphology was performed. Figure 1d,e shows the TEM images
In this work, we prepared a tangential hybrid nanostructure of Au/CuSe hybrids, which were produced at different reacting
through a facile hydrothermal method, containing three time. After 4 h of reaction, the pony-sized CuSe nanoplates can
components: Au nanosphere, CuSe ultrathin nanoplate, and be observed, which were attached on the one side of Au nano-
Pt nanoparticle, and investigated its prominent photocatalytic spheres (see Figure 1d). As the reacting time increased to 8 h,
hydrogen generation activity. In particular, 2D CuSe ultrathin the size of CuSe nanoplates enlarges, and monodispersed
nanoplate (average thickness of 5.5 nm) was grown along Au/CuSe hybrids are observed (see Figure 1e). Interestingly,
the tangent of Au nanosphere, and Pt nanoparticles were the Au/CuSe hybrids display uniform Janus-like morphology,
deposited on the Au nanosphere and CuSe nanoplate. In this indicating that CuSe nanoplates would be tangent to Au nano-
nanosystem, Au and CuSe are both plasmonic units for efficient spheres. The TEM image with low magnification in Figure S2,
light harvesting, hot electron generation, and near-field enhance- Supporting Information, shows that the yield of Janus-like
ment. Meanwhile, Pt nanoparticles are electron acceptors and Au/CuSe hybrids reaches 98%, demonstrating that the synthetic
cocatalysts for hydrogen production. Moreover, the intimate strategy is efficient and productive.
contact of the three components can generate many routes for To clearly investigate the multidimensional architecture of
charge transfer, thus guarantying the high utilization of dual- Au/CuSe hybrids, the TEM image with partial side view was
plasmon-induced hot electrons and photogenerated charges. presented. As shown in Figure 2a, the Au/CuSe hybrids labeled
Although Au, Pt, or Au/Pt nanocrystals were integrated with with red arrows suggest that the CuSe nanoplate is tangent to Au
2D materials for photocatalytic applications,[47–50] the metal nanosphere. The lateral morphology of Au/CuSe hybrids reveals
nanocrystals in such hybrids were usually randomly deposited that the CuSe nanoplates have an average thickness of about
on as-prepared 2D materials, and the integral structure of the 5.5 nm. Further characterizations on the detailed crystalline
hybrids was uncontrollable. To the best of our knowledge, this structure and composites of the Au/CuSe hybrids were carried
is the first time that the ternary Au/CuSe/Pt hybrid with strong out with high-resolution TEM (HRTEM). Figure 2b gives a top-
dual-plasmon resonance was integrated into a controllable and view HRTEM image of an Au/CuSe hybrid. A legible interface
desirable structural arrangement, in which plasmonic CuSe and distinct lattice fringes of Au and CuSe are observed, proving
ultrathin nanoplate was grown along the tangent of as-prepared the high crystallinity. The interplanar spacing on nanoplate is
Au nanosphere, and Pt nanoparticles were deposited both on Au calculated to 0.29 nm, corresponding to (006) plane of CuSe,
Figure 1. a) Schematic illustration of synthetic processes of CuSe nanoplates and Au/CuSe hybrids. TEM images of b) CuSe nanoplates, c) Au nano-
spheres, and Au/CuSe hybrids generated after reacting d) 4 h and e) 8 h.
which agrees well with previous works.[34,36,37] The side-view and the plasmon peak of CuSe nanoplates blue-shifts to
HRTEM image of Au/CuSe hybrids in Figure 2c shows the 1060 nm. We compared the extinction spectra of Au/CuSe hybrids
lattice plane distance of 0.24 nm, corresponding to (111) plane and physical mixture of Au and CuSe (see Figure S3, Supporting
of Au. Interestingly, the distinct layered structure of CuSe nano- Information). Interestingly, the two kinds of plasmon resonance
plate is observed. The thickness of the CuSe nanoplate is about are much stronger than that of physical mixture of Au and CuSe,
5.5 nm, which corresponds to about three-unit cells.[34] In addi- indicating strong plasmon coupling between Au and CuSe.
tion, the X-ray diffraction (XRD) pattern of Au/CuSe is shown in The photocatalytic hydrogen generation activity of Au/CuSe
Figure 2d, and the diffraction peaks located at 38.3 , 44.4 , 64.2 , tangential hybrids was investigated using Na2SO3 and Na2S
and 77.5 are assigned to the (111), (200), (220), and (311) planes aqueous solution as sacrificial reagents with visible light
of Au with the face-centered cubic (fcc) structure, respectively (λ > 420 nm) irradiation. For comparison, the photocatalytic
(PDF#65-8601). The diffraction peak located at 32.3 is consis- activities of pure CuSe nanoplates and physical mixture of Au
tent with the (006) plane of hexagonal CuSe (PDF#34-0171). and CuSe were also tested. As shown in Figure 3b, nanoplates
The dual-plasmon resonance of Au/CuSe tangential hybrids possess a low hydrogen generation activity, which is about
was tracked by testing the UV–visible and near-infrared (VIS–NIR) 0.67 mmol g1 after 7 h of reaction. The physical mixture of
extinction spectra. As shown in Figure 3a, initial Au nanospheres Au and CuSe has a slightly higher hydrogen generation, reaching
have a sharp plasmon peak located at 522 nm, and pure CuSe 0.82 mmol g1 with the same reaction time. Interestingly, the
nanoplates present a broad plasmon band in NIR region. After Au/CuSe tangential hybrids exhibit significant enhancement
the CuSe nanoplates were grown along the tangential direction of hydrogen generation activity, which reaches 3.77 mmol g1
of Au nanospheres (4 h of reaction), the plasmon peak of Au that is 5.6 and 4.6 times of CuSe and physical mixture of Au
red-shifts to 536 nm due to dielectric constant increasing caused and CuSe, respectively.
by CuSe. Meanwhile, the plasmon band of CuSe nanoplates The 2D CuSe ultrathin nanoplates possess unique thickness-
appears. After 8 h of reaction, the CuSe nanoplates enlarged, dependent features for photocatalytic hydrogen evolution, such
leading to the plasmon peak of Au further red-shifts to 542 nm as high specific surface areas and abundant surface-active sites.
The photocatalytic activity under the irradiation at the selected

wavelengths around the plasmonic peaks was measured to
further identify the dual-plasmon-enhanced photocatalysis.
As shown in Figure 3c, with a light irradiation of 550 and
950 nm, the Au/CuSe tangential hybrids exhibit higher photoca-
talytic hydrogen generation rate than the physical mixture of Au
and CuSe. The enhancement factor at 550 nm is about three
times, whereas the enhancement factor at 950 nm is about six
times, indicating the stronger plasmon-enhanced effect around
the plasmon resonance of CuSe. The local electric field distribu-
tion of Au/CuSe tangential hybrids was calculated to reveal the
underlying mechanism of the different enhancement ratios at
different wavelengths irradiation. As shown in Figure 3d–g, at
the plasmon resonance of Au, the strong local electric field is
found around the nanosphere (see Figure 3d,e), indicating
the high concentrations of hot electrons on the surface of Au
nanosphere. These hot electrons can be transferred to CuSe
nanoplates at the interface of Au and CuSe. At the plasmon
resonance of CuSe (see Figure 3f,g), much stronger local electric
field is found around the interface of Au and CuSe, indicating
much stronger interfacial local electric field coupling. This
electric field coupling not only enhances the light absorption of
Au/CuSe, but also excites more electron–hole pairs in CuSe
nanoplates, thus greatly enhancing the photocatalytic hydrogen
generation.
Subsequently, we deposited Pt nanoparticles on Au/CuSe
tangential hybrids through a hydrothermal method, in which
ascorbic acid was used as reductant and K2PtCl6 was used as
precursor (see Figure 4a). Figure 4b,d exhibits the TEM images
of the ternary Au/CuSe/Pt hybrids, illustrating that Pt nano-
particles with an average diameter of about 2 nm are randomly
deposited on Au nanospheres and CuSe nanoplates. Meanwhile,
the tangential architecture of Au/CuSe hybrids is well main-
tained (a clear comparison is presented in Figure S4,
Supporting Information). In addition, the high-angle annular
dark field scanning transmission electron microscopy (HAADF-
Figure 2. a) Partial lateral TEM image of Au/CuSe tangential hybrids. STEM) was performed to clearly reveal the 3D morphology of
HRTEM images of Au/CuSe hybrids obtained in b) top view and c) side Au/CuSe/Pt hybrids. As shown in Figure 4c, the architecture
view. d) XRD pattern of Au/–CuSe hybrids. of Au/CuSe/Pt hybrid is intuitively confirmed, in which the
CuSe nanoplate was grown along the tangent of Au nanosphere,
and Pt nanoparticles were deposited on Au and CuSe.
Meanwhile, the intense plasmon resonance of CuSe also benefits The HRTEM image of Au/CuSe/Pt hybrid is presented in
hydrogen production. The lowest hydrogen production rate of Figure S5, Supporting Information, in which the interplanar
CuSe nanoplates is mainly caused by the fast recombination spacing of 0.23 nm corresponds to the (111) plane of Pt. The
of the photoexcited electron–hole pairs and relative weak visible XRD pattern of Au/CuSe/Pt hybrids is shown in Figure 4e,
light absorption. For Au/CuSe hybrids, the photocatalytic activity and the phases of Au, CuSe, and Pt are observed. The extinction
is higher than pure CuSe and physical mixture of Au and CuSe, spectrum of Au/CuSe/Pt hybrids is shown in Figure 4f. In com-
indicating that the dual-plasmon coupling as well as synergistic parison with Au/CuSe hybrids, both the plasmon bands of Au
effect between plasmon and exciton play important roles in and CuSe were broadened. The plasmon peak of Au red-shifts
enhancing the hydrogen production rate. The dual-plasmon to 612 nm, whereas the plasmon peak of CuSe blue-shifts to
coupling between CuSe and Au can induce strong VIS–NIR light 954 nm, indicating that Au/CuSe/Pt hybrids have broad and
absorption for Au/CuSe hybrids, which would be the most intense light absorption in the UV–VIS–NIR region.
important factor for enhancing the hydrogen production rate. The photocatalytic activities of Au/CuSe/Pt hybrids and refer-
Meanwhile, the dual-plasmon-induced energy transfer, including ential samples were tested to reveal the synergistic effect of Pt for
resonant energy transfer, and hot electrons generation and injec- enhancing hydrogen production. As shown in Figure 4g, the
tion, can accelerate the reaction of hydrogen generation.[52–54] hydrogen production rate of Au/CuSe/Pt hybrids reaches
Moreover, the interfacial charge transfer between CuSe and Au 4.18 mmol h1 g1, which is 9.7 and 7.8 times that of Pt/CuSe
results in effective charge separation, which can improve the life- (TEM image, Figure S6, Supporting Information) and Au/CuSe
time of carries, thereby enhancing the hydrogen production rate. hybrids, respectively. Figure 4h displays the hydrogen production
Figure 3. a) Measured extinction spectra of CuSe nanoplates, Au nanospheres, and Au/CuSe generated at 4 and 8 h. b) Photocatalytic hydrogen genera-
tion activities of CuSe and Au/CuSe and physical mixture of Au nanospheres and CuSe nanoplates. c) Comparison of the hydrogen production rates of
Au/CuSe and physical mixture of Au and CuSe irradiated with different wavelengths. Calculated local electric field distribution of Au/CuSe tangential
hybrid at the plasmon resonance of d,e) Au and f,g) CuSe. d,f ) 3D view. e,g) Sectional view.
of Au/CuSe/Pt, evaluating every 5 h without renewing the sacrifi- still observed around the interface between Au and CuSe.
cial agents. The photocatalytic evolution rate is well maintained Meanwhile, the local electric field around Pt nanoparticles
after four cycling tests, indicating excellent catalytic stability. (on Au and CuSe) is enhanced, theoretically indicating that
The TEM image of Au/CuSe/Pt after photocatalytic tests was the plasmon-induced electrons on CuSe could be transferred
shown in Figure S7, Supporting Information, and the morphology to Pt, thus enhancing the photocatalytic activity.
had negligible change, indicating good structural stability. Accompanying with Pt nanoparticles, the photocatalytic rate of
To reveal the plasmon-enhanced mechanism of high photoca- Pt/CuSe is obviously enhanced, which is 4.5 times that of CuSe.
talytic activity of Au/CuSe/Pt tangential hybrids, apparent quan- This is because Pt nanoparticles can be used as co-catalysts and
tum efficiency (AQE) of hydrogen generation was tested using active sites for hydrogen production; also, they could suppress
monochromatic light irradiation. As shown in Figure 5a, AQE the recombination of electron–hole pairs due to its low Fermi
of Au/CuSe/Pt matches well with its extinction spectrum, level. The photocatalytic activity of ternary Au/CuSe/Pt is 7.8
suggesting that the high photocatalytic hydrogen production times that of binary Au/CuSe, which is higher than the photo-
was mainly enhanced by the dual plasmonic excitation of Au catalytic activity enhancement factor of Pt/CuSe to CuSe
and CuSe. In addition, the photoelectrochemical experiments (4.5 times). This reveals that the synergistic effect induced by
were performed using a three-electrode system to explain the a three-component system plays an important role in enhancing
dual-plasmon-enhanced photocatalysis (Figures S8, Supporting the photocatalytic activity. Ternary Au/CuSe/Pt hybrid possesses
Information). The Au/CuSe/Pt electrode exhibits the largest two plasmonic units; one is 2D semiconductor, and the other is
photocurrent, which is consistent with the results of hydrogen Au nanosphere. Meanwhile, the three components of Au, Pt, and
generation tests, indicating that the most charge carriers were CuSe have direct contact with each other; thereby, there exist
produced. The local electric field distribution of Au/CuSe/Pt several electron-transfer processes in this hybrid, which may be
was further calculated to explain the highest photocatalytic responsible for the enhanced photocatalytic activity. Ultrafast
activity. As displayed in Figure 5c,d, the plasmon resonance of transient absorption measurements probed at different wave-
Au greatly enhanced the electric field around the Pt nanoparticles lengths were used to investigate the possible electron-transfer
(deposited on Au and CuSe nanoplates), theoretically revealing processes in ternary Au/CuSe/Pt hybrid. Meanwhile, the possi-
plasmon-induced electrons transfer from Au to Pt. Figure 5e,f ble inner electron-transfer processes and band structure
exhibits the local electric field distribution at plasmon resonance alignment in the three-component hybrids are schematically
of CuSe, and the strong local electric field coupling is shown in Figure 5h and Figure S10, Supporting Information.
Figure 4. a) Schematic illustration of the deposition of Pt nanoparticles on Au/CuSe hybrid. b) TEM image of Au/CuSe/Pt hybrids. c) HAADF-STEM and
d) TEM images of a single Au/CuSe/Pt tangential hybrid. e) XRD pattern of Au/CuSe/Pt hybrids. f ) Extinction spectra of Pt/CuSe, the initial Au/CuSe, and
resultant Au/CuSe/Pt tangential hybrids. g) Comparison of the hydrogen production rate of Au/CuSe/Pt, Au/CuSe, and Pt/CuSe hybrids. h) Photocatalytic
cycling tests of Au/CuSe/Pt under visible light irradiation.
As shown in Figure 5f, upon 560 nm excitation, the decay curve In addition, the CuSe nanoplates also have intense plasmon
of Au with fast and slow processes reveals the relaxation dynam- absorption in NIR region. The transient absorption decay probed
ics of plasmon-induced hot electrons. The fast process is attrib- at 900 nm for CuSe, Au/CuSe, and Au/CuSe/Pt hybrids was
uted to the electron–phonon scattering in Au core, and the slow tested to verify the hot electron generated on the CuSe transfer-
process belongs to the eventual charge recombination process. ring process. As shown in Figure 5g, Au/CuSe/Pt displayed
The decay rate of Au/CuSe is faster than Au, indicating that fastest decay rate followed by Au/CuSe and CuSe, revealing that
the plasmon-induced hot electrons in Au nanospheres could the plasmon-induced hot electrons in CuSe nanoplate could
be quickly transferred into CuSe ultrathin nanoplates (Path 1, inject into Au nanosphere and Pt nanoparticles (Paths 3 and 4,
Figure 5h). This process could be widely understood as hot Figure 5h). Besides, the photogenerated electrons in the
electrons injection from metal to semiconductor.[52–54] Ternary conduction band of CuSe might be transferred to Au and Pt
Au/CuSe/Pt displayed fastest decay time compared with Au due to their intimate contact. These enriched electron-transfer
and Au/CuSe, demonstrating that the hot electrons generated on processes could greatly improve the utilization efficiency of
Au nanospheres can also be transferred to Pt (Path 2, Figure 5h). dual-plasmon-induced electrons and photogenerated charges,
Figure 5. a) AQE% for hydrogen generation of Au/CuSe/Pt tangential hybrids as a function of excitation wavelength. Calculated local electric field distri-
bution for Au/CuSe/Pt tangential hybrid at the plasmon peaks of b,c) Au and d,e) CuSe. b,d) 3D view. c,e) Sectional view. Normalized optical transmis-
sion change as a function of time delay probed at different wavelengths for Au, CuSe, Au/CuSe, and Au/CuSe/Pt. f ) Probed at 560 nm for Au, Au/CuSe,
and Au/CuSe/Pt. g) Probed at 900 nm for CuSe, Au/CuSe, and Au/CuSe/Pt. h) Schematic diagrams of the possible electron-transfer processes in Au/
CuSe/Pt tangential hybrid during the photocatalytic hydrogen reaction.
thus enhancing the photocatalytic activity of Au/CuSe/Pt ternary hybrid, plasmonic CuSe ultrathin nanoplate (5.5 nm)
tangential hybrids. was grown along the tangent of Au nanosphere, and Pt nanopar-
The Au/CuSe/Pt hybrids reported in this work display follow- ticles were deposited in situ on CuSe nanoplate and Au nano-
ing advantages for photocatalytic hydrogen production. First, sphere. AQE tests indicated that the dual-plasmon resonance
both Au nanospheres and CuSe nanoplates are plasmonic units ranging from visible to near-infrared contributes significantly
for light harvesting, which endows Au/CuSe/Pt with broad and to the outstanding photocatalytic activity of Au/CuSe/Pt hybrids.
strong light absorption in VIS–NIR region. Second, the strong The strong local electric field coupling at the interface of Au
local electric field coupling between Au nanospheres and and CuSe revealed by theoretical simulation is conducive to light
CuSe nanoplates can greatly enhance the light absorption and absorption and electron–hole pair generation. Meanwhile, the
excite more electron–hole pairs in CuSe. Third, the affluent enriched electron-transfer pathways in the three-component
electron-transfer processes caused by the three-component Au/CuSe/Pt nanosystem facilitate maximal utilization of dual-
system lead to the high-effective utilization of plasmon-induced plasmon-induced hot electrons and photoexcited charges.
hot electrons and photogenerated charge, which contribute Moreover, the abundant surface-active sites induced by the
significantly to the prominent photocatalytic hydrogen evolution tangential architecture and CuSe ultrathin nanoplates are also
activity of Au/CuSe/Pt hybrids. Finally, the tangential architec- beneficial to the photocatalytic hydrogen generation of Au/
ture of Au/CuSe/Pt, in which CuSe nanoplate is tangent to CuSe/Pt hybrids. Our findings could inspire the further develop-
Au nanosphere and Pt nanoparticles are deposited both on Au ment of advanced hetero-nanomaterials based on dual-plasmon
and CuSe, can induce abundant surface-active sites, thus enhanc- coupling, and the materials we prepared may be used in photo-
ing for the hydrogen reduction reaction. electric devices and other applications.
3. Conclusion 4. Experimental Section

In summary, Au/CuSe/Pt hybrids with a tangential architecture Reagents: Chloroauric acid (HAuCl4·4H2O, 99.99%), potassium chloro-
and dual-plasmon resonance were established for efficient platinate (K2PtCl6, 99.5%), sodium hydroxide (NaOH, 99.7%), L-ascorbic acid
photocatalytic hydrogen production from water splitting. In the (99.7%), sodium sulfite (Na2SO3, 99.5%), sodium sulfide (Na2S, 99.5%),
sodium borohydride (NaBH4, 96.0%), cupric acetate (99.5%), sodium used in the simulations. CuSe nanoplate was taken to be a hexagonal plate
iodide (NaI, 99.5%), hexamethylenetetramine (99.0%), and selenium with a side length of 26 nm and a thickness of 6 nm, and the edges of the
powder (Se, 99.9%) were purchased from Sinopharm Chemical Reagent nanoplate were smoothed by fillet whose radius was 5 nm. Au nanosphere
Co. Ltd. (Shanghai, China). Hexadecyltrimethylammonium bromide was taken to be a sphere with a radius of 10 nm, and Pt nanoparticles were
(CTAB, 99.0%) was purchased from Amresco, Inc. (America). taken as a sphere with a radius of 1 nm, which were randomly distributed
Deionized water with a resistivity of about 18.25 MΩ cm was used as on CuSe nanoplate and Au nanosphere.
the solvent in all experiments. Sample Characterization: The TEM images were obtained with a JEOL
Synthesis of Au/CuSe Hybrids and CuSe Nanoplates: CTAB-stabilized Au 2100 operated at 200 kV. HRTEM images and energy dispersive spectros-
nanospheres were prepared using a seed-mediated method as reported copy (EDS) were performed using a JEOL 2010 FET microscope operated
previously.[55] Au nanospheres were centrifuged at 10 000 rpm for at 200 kV accelerating voltage. XRD spectra patterns were obtained on a
15 min and re-dispersed in water for three times before use. To grow Bruker D8 advance X-ray diffractometer with Cu-Kα irradiation. The extinc-
CuSe nanoplates along the tangent of Au nanospheres, selenium powder tion spectra were tested using UV–VIS–NIR spectrophotometry (TU1810,
was first dissolved in NaBH4 aqueous solution to obtain 0.1 M of NaHSe Beijing Purkinje General).
solution. Subsequently, 1 mL of hexamethylenetetramine (0.1 M), 1 mL of
L-ascorbic acid (0.1 M), and 1 mL of CTAB (0.2 M) were added into 5 mL of
as-prepared Au nanospheres. Then, 0.06 mL of freshly prepared NaHSe Supporting Information
and 0.06 mL of cupric nitrate (0.1 M) solution were added to the mixture.
The mixture solution was kept at 90 C in a vacuum oven for 8 h. The prod- Supporting Information is available from the Wiley Online Library or from
ucts were centrifuged at 8000 rpm for 5 min and re-dispersed in water for the author.
further use. CuSe nanoplates were prepared through a similar process
mentioned earlier without adding Au nanospheres.
Synthesis of Au/CuSe/Pt and Pt/CuSe Hybrids: In a typical procedure, Acknowledgements
0.1 mL of NaI (10 mM) was added into 5 mL of CTAB (0.2 M) aqueous
solution. Then, 3 mL of as-prepared Au/CuSe and 0.5 mL of AA (0.1 M) L.M., D.-J.Y., and X.-P.S. contributed equally to this work. This research
were added to the mixture solution. The reaction mixture was kept at was funded by the National Natural Science Foundation of China
70 C for 1 h; then, 0.05 mL of K2PtCl6 (5 mM) was added. The mixture (11574241, 11804257, 11904270, 11904332), Natural Science Foundation
was kept at 70 C for another 3 h. The final product was centrifuged, of Hubei Province (2018CFB106), Hubei Provincial Department of
washed, and re-dispersed in water for further test. Pt/CuSe hybrids were Education (D20151506), and Scientific Research Foundation (18QD24
synthesized by a similar process, in which Au/CuSe hybrids were replaced and 18QD25) of Wuhan Institute of Technology.
by CuSe nanoplates.
Photocatalytic Activity for Hydrogen Production: The visible light photo-
catalytic hydrogen production tests were conducted with a commercial
photocatalytic evaluation system. Typically, 50 mg of photocatalyst
Conflict of Interest
powders were dispersed in 50 mL of aqueous solution containing The authors declare no conflict of interest.
Na2SO3 (0.25 M) and Na2S (0.35 M) as sacrificial reagents. The light source
was a 300 W Xenon lamp equipped with an ultraviolet cutoff filter
(λ > 420 nm). The temperature of the suspension was maintained at room
temperature using an external water-cooling system. The amount of hydro- Keywords
gen gas was automatically analyzed by online gas chromatograph
(Tianmei GC-7920). The AQE was measured using a series of quartz Au/CuSe tangential hybrids, dual plasmon, local electric field coupling,
bandpass filters to obtain the monochromatic light. Photo flux of the photocatalytic hydrogen generation
incident light was tested by a Ray virtual radiation actinometer.
Photoelectrochemical Measurements: Photocurrent measurements were Received: August 28, 2019
performed on electrochemical workstation with a standard three-electrode Published online: September 30, 2019
system. The counter electrode and the reference electrode were Pt and
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PT Decorated Au Nanosphere CuSe Ultrathin Nanoplate Tangential Hybrids For Efficient

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Pt Decorated (Au Nanosphere)/(CuSe Ultrathin Nanoplate)

ideal photocatalyst, it should simulta-

The photocatalytic activity under the irradiation at the selected

3. Conclusion 4. Experimental Section

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