Efficient photoredox conversion of alcohol to aldehyde and H2 by heterointerface engineering of bimetal-semiconductor hybrids

Article abstract of DOI:10.1039/c8sc05813j

Controllable and precise design of bimetal- or multimetal-semiconductor nanostructures with efficient light absorption, charge separation and utilization is strongly desired for photoredox catalysis applications in solar energy conversion. Taking advantage of Au nanorods, Pt nanoparticles, and CdS as the plasmonic metal, nonplasmonic co-catalyst and semiconductor respectively, we report a steerable approach to engineer the heterointerface of bimetal-semiconductor hybrids. We show that the ingredient composition and spatial distribution between the bimetal and semiconductor significantly influence the redox catalytic activity. CdS deposited anisotropic Pt-tipped Au nanorods, which feature improved light absorption, structure-enhanced electric field distribution and spatially regulated multichannel charge transfer, show distinctly higher photoactivity than blank CdS and other metal-CdS hybrids for simultaneous H₂ and value-added aldehyde production from one redox cycle.

Full text of DOI:10.1039/c8sc05813j

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Efficient photoredox conversion of alcohol to aldehyde and H2 by
heterointerface engineering of bimetal-semiconductor hybrids†
Chuang Han,ab Zi-Rong Tang,b Junxue Liu,c Shengye Jin,*c and Yi-Jun Xu*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Controllable and precise design of bimetal- or multimetal-semiconductor nanostructures with efficient light absorption,
charge separation and utilization is strongly desired for photoredox catalysis applications in solar energy conversion.
Taking advantage of Au nanorods, Pt nanoparticles, and CdS as plasmonic metal, nonplasmonic co-catalyst and
semiconductor respectively, we report a steerable approach to engineer the heterointerface of bimetal-semiconductor
hybrids. We show that the ingredient composition and spatial distribution between bimetal and semiconductor
significantly influence the redox catalytic activity. The CdS deposited anisotropic Pt-tipped Au nanorods, which features
the improved light absorption, structure-enhanced electric field distribution and spatially regulated multichannel charge
transfer, shows distinctly higher photoactivity than blank CdS and other metal-CdS hybrids for simultaneous H2 and value-
added aldehyde production from one redox cycle.
www.rsc.org/
recent research has predominantly focused on charge
separation and transfer mainly occurring at the plasmonic
metal domains (i.e., SPR-induced sensitization effect),25-27 and
Introduction
Harvesting solar energy to drive artificial photosynthesis for
the production of value-added chemicals and renewable
energy is a promising strategy to solve the growing worldwide
energy crisis.1-5 However, the solar-to-chemical conversion
efficiency of semiconductor is often limited by their finite light
absorption and/or slow charge separation rates and reaction
kinetics.6-10 Integrating different functional materials into a
single hybrid structure with precise design holds great promise
for constructing efficient composite photocatalysts owing to
the synergistic properties induced by the interactions between
these components in an integrative ensemble.5, 11-16
Bimetallic nanostructures, coupling surface plasmon
resonance (SPR, Scheme S1) functionality with efficient co-
catalytic effect, could be an ideal candidate to simultaneously
modulate the photoabsorption and steer the multichannel
charge separation/transfer and reaction kinetics of
semiconductor.17-21 The design of effective bimetal-
semiconductor composite photocatalysts requires the rational
understanding of structural design principle, because the
randomly hybridizing counterparts would often shield the SPR
intensity and local electric field of plasmonic metal or weaken
the net photoabsorption of semiconductor.22-25 In addition,
the quantum efficiency over such systems is still relatively low
in contrast to those by semiconductor photoexcitation. To
obtain a high photocatalytic activity, the structural design of
special composite catalysts to synergistically utilize SPR
enhancement mechanism and band-gap photoexcitation of
semiconductor is desirable.28, 29 However, thus far, it is still
unclear how the composition and structural arrangement of
plasmonic-nonplasmonic bimetal hybrids comprehensively
affect their interactions with semiconductor and the
subsequent band alignment, charge transfer dynamics, local
electric field distribution and redox catalysis performance.
Herein, we report a controllable way to design bimetal-
semiconductor hybrids with different heterointerfaces for
progressively improved redox catalysis conversion of alcohol
to H2 and aldehyde under visible-near-infrared (Vis-NIR) light
irradiation. Au nanorods (NRs) and Pt nanoparticles (NPs) are
promising metalic nanocrystals platform for fabricating metal-
semiconductor hybrids due to their tunable longitudinal-SPR
absorption in the near-infrared (NIR) region and high efficiency
for catalysis proton reduction reaction, respectively.13, 30-34 In
this regard, we chose Au NRs and Pt NPs to form the plasmonic
bimetal component. CdS, a well-known visible (Vis) light
responsive photocatalyst with a direct band-gap of around 2.4
35-38
eV,8,
is chosen as the semiconductor component.
Intergrating co-catalytic factor with semiconductor
photoexication and SPR resonance modes in different optical
response region by rational assembly of nonplasmonic Pt NPs
and semiconductoron CdS on the surface of Au NRs, can
provide the spatial transfer multichannel for electrons and
boost the local electric field, promoting the generation and
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migration of electron-hole charge carriers. As a result, the CdS
deposited anisotropic Pt-tipped Au NRs (Au-Pt@CdS), which
features the multiple metal-semiconductor and metal-metal
heterojunctions, exhibits distinctly higher photoactivity than
blank CdS and other metal-CdS hybrids counterparts for
photocatalytic conversion of alcohol to aldehyde and H2 by
simultaneous utilization of photogenerated holes and
electrons in one redox cycle. Resorting to electric field
simulations, transient absorption spectroscopy and multiple
control experiments, it is demonstrated that the redox
photoactivity is highly dependent on the ingredient
composition and spatial distribution of metal component
because they play a significant role in affecting multiple
electron transfer pathways and local electric field
enhancement.
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DOI: 10.1039/C8SC05813J
Results and discussion
Fig. 1 SEM images of (a) Au NRs, (b) Au-Pt, and (c) Au@Pt, scale bar, 200 nm. The insets
of (a-c) show TEM images of corresponding samples, scale bar, 20 nm. TEM images of
(d) Au@CdS, (e) Au-Pt@CdS and (f) Au@Pt@CdS, scale bar, 200 nm. Elemental
mapping results of (g) Au-Pt@CdS and (h) Au@Pt@CdS.
The fabrication process is based on progressively seed-
mediated growth, as illustrated in Scheme 1. The stronger
interaction between the cetyltrimethylammonium bromide
(CTAB) surface-capping molecules and the side facets of Au
NRs results in the higher packed density of CTAB at the sides
than that at the ends of Au NRs.24, 25 By taking advantage of
this anisotropic surface structure, Pt NPs were firstly
selectively deposited on the tips of Au NRs seeds for
preparation of anisotropic Pt-tipped Au NRs (Au-Pt). The
spatial distribution of Pt on the Au NRs surface depends on the
surface-capping molecules. Pt-covered Au NRs (Au@Pt) can be
synthesized by decreasing the concentration of CTAB
molecules. The Au-based NRs were subsequently used as
seeds for assembly of semiconductor CdS via a facile and
controllable refluxing process. It should be noticed that our
synthesis reaction is performed at low temperature (85 °C) and
in the absence of metal ion sources (e.g., Ag+ or Cu2+) as a
diameter and length of original Au NRs are 29.0 and 92.5 nm,
respectively (Fig. 1a and Fig. S1). After the growth of Pt onto
the tips of Au NRs, the smooth ends of Au NRs become
gibbous, while the surface at the side of Au NRs remains
almost unchanged (Fig. 1b and Fig. S2). The average diameter
at the middle of Au-Pt NRs is 29.1 nm, and the average length
is increased to 114.0 nm. These results suggest that Pt tends to
anisotropically deposit at the two ends of Au NRs. Fig. 1c and
Fig. S3 show the morphology of Au@Pt with an average
diameter of 33.2 nm and length of 107.9 nm, which are
enclosed by the Pt shell.
The morphology information of CdS deposited Au NRs
(Au@CdS), CdS deposited Pt-tipped Au NRs (Au-Pt@CdS) and
CdS deposited Pt-covered Au NRs (Au@Pt@CdS) are disclosed
“bridge” between Au NRs and CdS to achieve the
in Fig. 1d-f and Fig. S4. No noticeable structural deformation of
40
heterogrowth,39,
which can prevent the Au NRs from
Au-based seeds can be discerned after depositing CdS
nanoshells, which should benefit from the mild reaction
process at a low temperature. For Au@CdS, we can clearly see
undesired reshaping in the wet-chemistry growth process.
The samples obtained in each growth stage were
characterized using scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) analysis. The average
from Fig. 1d and Fig. S4a-c that the Au NRs core with
hemispherical ends are coated with a loose and porous CdS
semiconductor layer in thicknesses of 15-20 nm. TEM images
of Au-Pt@CdS (Fig. 1e) and Au@Pt@CdS (Fig. 1f) indicate their
similar overall shape to Au@CdS. However, the bimetal cores
in Au-Pt@CdS and Au@Pt@CdS respectively show the convex
(Fig. S4d-f) and bar-like (Fig. S4g-i) shape. Elemental mapping
analysis on Au-Pt@CdS (Fig. 1g) discloses that the Pt is located
at the ends of Au NRs, further confirming the tip-coated
morphology of Au-Pt core in Au-Pt@CdS. Elemental mapping
study for Au@Pt@CdS indicates the layers of Pt and CdS shells
are both isotropically deposited on the entire surface of Au
NRs (Fig. 1h). The morphology of blank CdS was also analyzed
(Fig. S5), suggesting that blank CdS are composed of tiny NPs.
X-ray diffraction (XRD) patterns of blank CdS and metal-CdS
Scheme
1 Schematic flowchart illustrating the controllable preparation of CdS
hybrids are shown in Fig. 2a, in which the diffraction peaks of
hexagonal phases CdS (JCPDS, No. 41-1049) and cubic phases
deposited Pt-tipped Au NRs (Au-Pt@CdS), CdS deposited Au NRs (Au@CdS) and CdS
deposited Pt-covered Au NRs (Au@Pt@CdS).
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on the photoactivity and determined the sampleVwiewithArtoicpletOimnlinael
photoactivity, as shown in Fig. S7a
. ThDeOdI:ir1e0c.1t03p9h/oCt8oSCa0ct5i8v1i3tyJ
-
c
comparison with the H2 and BAD production rates over the
samples with the optimal components proportion is shown in
Fig. 2d. Notably, the molar ratio of reduction product (H2) and
oxidation product (BAD) is calculated to be ca. 1.0, suggesting
a stoichiometric dehydrogenation reaction. The fine control of
the heterointerface of metal-semiconductor composites can
result in the progressively optimal photoactivity. Blank Au-Pt
and CdS show very low activity for H2 and BAD production due
to the fast recombination of electron-hole pairs.11, 12, 20, 31 For
binary Au@CdS, the H2 evolution rate is enhanced to 53.2
μmol h-1. After coupling co-catalyst Pt with Au@CdS, the H2
evolution rates over ternary Au@Pt@CdS and Au-Pt@CdS
reach to 96.6 μmol h-1 and 153.0 μmol h-1, respectively, which
are about 13.4 and 21.2 times as high as that over blank CdS
(7.2 μmol h-1). Notably, the anisotropic Au-Pt@CdS exhibits
higher H2 and BAD production rates than Au@CdS and
Au@Pt@CdS, implying that the photoactivity enhancement of
bimetal-semiconductor composites is not only dependent on
the ingredient composition, but also affected by the spatial
distribution of metal components. For comparison, we also
investigated the photoactivity of CdS supported Au-Pt NRs (Au-
Pt/CdS, Fig. S7d) and the result shows that the photoactivity of
such supported Au-Pt/CdS is much lower than that of Au-
Pt@CdS, which manifests that the core-shell configuration can
strengthen the interfacial contact between metal and
semiconductor CdS, thereby facilitating the charge carriers
separation and transfer across the interfacial domain and
consequently boosting the photoactivity.
Fig. 2 (a) XRD patterns, (b) Raman spectra and (c) absorption spectra of CdS and metal-
CdS hybrids. The inset of (c) shows the normalized absorption spectra of Au, Au@Pt
and Au-Pt for comparison. (d) H2 and benzaldehyde (BAD) generation rate in the
photocatalytic conversion of benzyl alcohol (BA) under Vis-NIR light (λ > 420 nm)
irradiation over Au-Pt, CdS and metal-CdS hybrids. The insets of (d) show the formula
for photocatalytic conversion of BA and the corresponding structural models of the
samples.
Au (JCPDS, No. 65-8601) can be well identified. The
characteristic diffraction peaks of Pt are hardly observed due
to their relatively low content in the composites.41 Raman
spectra, as displayed in Fig. 2b, show that blank CdS exhibits
the Raman signals at 299 cm-1, 597 cm-1 and 890 cm-1, which
are identified as characteristic peaks of the longitudinal optical
(LO) phonons of CdS phase.42 In comparison with CdS, all of
these peaks are significantly intensified for CdS deposited
metal hybrids, suggesting an enhanced light-matter interaction
due to the strong electric field enhancement near the surface
of plasmonic Au-based NRs.42
The evolution of optical absorption spectra along with the
structural variation of the samples is displayed in Fig. 2c. The
raw Au NRs have two SPR absorption bands centered at 510
and 800 nm, which are respectively assigned to transverse-SPR
(T-SPR) and longitudinal-SPR (L-SPR) photoabsorption (inset of
Fig. 2c). After Pt is deposited on Au NRs, the L-SPR band red-
shifts to 833 and 865 nm for Au@Pt and Au-Pt, respectively. In
addition, the T-SPR band of Au@Pt slightly red-shifts to 527
nm, while almost no change occurs for that of Au-Pt, which is
probably due to the selective deposition of Pt onto the tips of
Au NRs for the Au-Pt sample.24 Both the T-SPR and L-SPR band
are further red-shifted after the semiconductor CdS is grown
onto Au@Pt and Au-Pt, resulting from the increase of
surrounding dielectric constant.31, 43 The blank CdS and metal-
CdS hybrids disclose the similar optical absorption threshold
located at 520 nm, which is corresponding to the optical band-
gap of about 2.4 eV in pristine CdS semiconductor. However,
the absorption of metal-CdS hybrids is higher than that of
blank CdS throughout the whole Vis to NIR region due to the
contribution from the SPR absorption of Au-based NRs.36, 43
We tested the samples as dual-function photocatalysts for
conversion of benzyl alcohol (BA) to H2 and benzaldehyde
(BAD) under Vis-NIR light (λ > 420 nm, Fig. S6) irradiation. We
initially studied the effects of different components proportion
The photoactivity enhancement and general applicability of
Au-Pt@CdS were further investigated by conversion of other
aromatic alcohols (R-PhCH2OH, R = OCH3, CH3, Cl and OH) with
different substituent groups. By taking the unsubstituted BA
(Fig. 2d) as reference, Fig. S8a-d indicate that the H2 and
aldehydes production rates are enhanced by electron-donating
substituents (R = OCH3 and CH3) and retarded by electron-
withdrawing groups (R = Cl and OH) for all photocatalysts. The
Au-Pt@CdS displays higher photoactivity than blank CdS and
other metal-CdS hybrids for conversion of these alcohols. In
addition, the photocatalytic performance of Au-Pt@CdS is
either comparable or superior to other similar coupled
reaction systems for simultaneous H2 and value-added
chemicals production (Table S1).
Fig. 3a shows the long-term photocatalytic performance of
the Au-Pt@CdS toward conversion of BA under Vis-NIR light
irradiation. After 5 h of irradiation, the conversion of BA is
about 80.1% and the selectivity for BAD reaches 94.0%. The H2
and BAD production rates display no obvious decrease during
four successive runs within 20 h. In addition, the morphology,
composition and crystalline structure of Au-Pt@CdS after
recycling photocatalytic reactions are similar to the fresh
sample (Fig. S9). These results indicate the good stability of
Au-Pt@CdS in our photocatalytic reaction conditions. To
understand the roles respectively played by semiconductor
and metal components of Au-Pt@CdS in the photoactivity
enhancement, we performed the wavelength-dependent
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to the plasmon-induced electrons transfer from Au to Pt and
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DOI: 10.1039/C8SC05813J
the serious plasmon damping effect of the continuous Pt
shell.23-25, 36 According to the simulation result, the maximum
value of electric field enhancement at the outside surface of
CdS for Au@CdS, Au-Pt@CdS and Au@Pt@CdS are about 15,
13 and 5, respectively. The enhanced electric field can improve
the light harvesting ability of the catalyst, and increase the
generation and separation rate of electron-hole pairs near the
surface of the semiconductor material.45-47 However, the trend
in electric field enhancement (i.e., Au@CdS > Au-Pt@CdS >>
Au@Pt@CdS) is inconsistent with that of photoactivity (i.e.,
Au-Pt@CdS > Au@Pt@CdS > Au@CdS). This indicates that in
addition to the effect of electric field enhancement factor on
the photoactivity of metal-semiconductor hybrids, other
factors should be simultaneously considered to account for the
difference in photoactivity enhancement.
We then investigated charge transfer dynamics in CdS and
metal-CdS hybrids by using ultrafast transient absorption (TA)
spectroscopy. Upon 370 nm excitation, a negative absorption
peak at about 500 nm corresponding to the ground state
bleach (GSB) signal of CdS component is formed due to the
band-filling by photoinduced electrons and holes (Fig. 3d and
Fig. S10). The recovery kinetics of this GSB reflects the charge
dissipating processes by recombination and/or charge transfer
Fig. 3 (a) Long-term photocatalytic conversion of BA using Au-Pt@CdS under Vis-NIR
light (λ > 420 nm) irradiation. (b) Absorption spectra of Au-Pt@CdS and apparent
quantum yield efficiency (AQY) of hydrogen evolution from BA under different
monochromatic lights. Error bars refer to the wavelength range of the incident light. (c)
Local electric field distributions of metal-CdS hybrids at L-SPR excitation calculated by
finite-difference time-domain method. (d) Transient absorption (TA) spectra of Au-
Pt@CdS with time delays after 370 nm excitation. (e) Comparison of the exciton bleach
recovery kinetics for CdS and metal-CdS hybrids probed at 503 nm and their
corresponding fits.
(Fig. 3e). In blank CdS, the recovery kinetics originates from
the recombination of electrons and holes and possible charge
trapping process into defects.15, 48 In the presence of metal
nanostructures, the kinetics become significantly faster. We
attribute this observation to the photoinduced electrons
transfer from CdS to the metal ingredient, as reported in
similar semiconductor-metal composites.11, 29, 49 In order to
quantitatively determine the electrons transfer rate, the
recovery kinetics were fitted by a biexponential function and
the electrons transfer rates were estimated by comparing the
charge transfer rate constant (kct, see Equation S1-3 and Table
S2).50 In comparison with blank CdS, the charge transfer rate
over binary Au@CdS is increased, which indicates an electrons
transfer channel from CdS to Au because the work function of
Au (5.10 eV) is larger than that of CdS (4.20 eV).51, 52 After the
Pt NPs (with work function of 5.40 eV) are deposited on Au
NRs, the kct of both Au@Pt@CdS and Au-Pt@CdS are further
enhanced. The highest kct value for Au-Pt@CdS signifies that
the Au-Pt bimetal nanostructure is more effective than Au@Pt
in facilitating the photoexcited charge transfer in the
photocatalytic system, due to the additional interfacial
electrons transfer channels from CdS to Au and to Pt
guaranteed by the direct contact and matched band alignment
among three components (Fig. S11).51, 52
experiment. As shown in Fig. 3b, the action spectrum of
apparent quantum yield efficiency (AQY) is in agreement with
the band-gap absorption of CdS component. This result reveals
that the photocatalytic conversion of BA to produce BAD and
H2 proceeds through the light absorption by semiconductor
CdS component instead of SPR excitation of Au-Pt bimetal.24, 44
Therefore, it is crucial to explore what is the specific role of
plasmonic Au and nonplasmonic Pt in improving the
photoactivity of semiconductor CdS, and what kind of
contribution of the SPR excitation is associated with bimetallic
Au-Pt in influencing charge carriers separation photogenerated
from CdS in Au-Pt@CdS.
Since electric field distribution and intensity are related to
the SPR enhancement,25, 45, 46 we simulated the electric field
(|E|/|E0|) distribution around different metal-CdS hybrids,
aiming to ascertain the region of electric field enhancement
upon SPR excitation and its possible contribution to the
photoactivity enhancement. As shown in Fig. 3c, differing from
strong electric field distribution at both ends of binary
Au@CdS, the ternary Au@Pt@CdS sample exhibits weak
electric field enhancement. When the continuous Pt shell
encapping the entire surface of Au NRs in Au@Pt@CdS is
replaced by discrete Pt selectively tipped onto the two ends of
Au NRs in Au-Pt@CdS, the electric field enhancement around
the surface of Au-Pt@CdS is greatly boosted. The weakest
electric field enhancement of Au@Pt@CdS could be ascribed
To study the effect of SPR excitation on photoactivity
enhancement, we performed wavelength-control experiment
over Au-Pt@CdS under selective photoexcitation of plasmonic
Au-Pt component (Fig. S12a).31, 53 It is seen from Fig. S12b that
the Au-Pt@CdS hybrids show only trace photoactivity under
SPR excitation alone, indicating the effect of hot electrons
injection from Au-Pt to CdS on the photoactivity is negligible.
When we used the photon energy at 570 nm to excite the T-
SPR of Au-Pt@CdS in TA measurement, the sample shows no
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signal corresponding to excitation and relaxation kinetics (Fig.
S12c), which further confirms the absence of hot electrons
transfer process. Thus, the SPR enhancement mechanisms
should be interpreted in terms of electric field effect.45 In
addition, control experiments under selective photoexcitation
of CdS or simultaneous photoexcitation of CdS and Au-Pt (Fig.
View Article Online
DOI: 10.1039/C8SC05813J
S13a
) disclose that the Au-Pt@CdS exhibits enhanced
photoactivity as compared to bare CdS under both irradiation
conditions, and the photoactivity enhancement is more
prominent under simultaneous photoexcitation of CdS and Au-
Pt component (Fig. S13b). We also prepared nonplasmonic Pt-
loaded
CdS
(Pt-CdS)
through
the
well-reported
photodeposition method.44, 54 The photocatalytic activity of
nonplasmonic Pt-CdS is much lower than that of plasmonic Au-
Pt@CdS under Vis-NIR light irradiation (Fig. S13c).
The above joint results signify that the promoted
photoactivity of Au-Pt@CdS is induced by the synergistic
coupling of the band-gap photoexcitation of semiconductor
CdS with the electric field enhancement and the electrons sink
effect of Au-Pt bimetal, as depicted in Fig. 4a 55, 56
.
Specifically,
when Au-Pt@CdS ternary heterostructure is illuminated by Vis-
NIR light (λ 420 nm), CdS component can harvest short-
wavelength visible light (420 nm
>
<
λ < 520 nm), yielding
electron-hole charge carriers (e--h+). Meanwhile, the SPR
excitation of plasmonic Au-Pt bimetal by longer-wavelength
light irradiation provides extra electric field enhancement to
improve the photoabsorption, and promote the generation
Fig.
4
(a) Schematic illustration of the energy band alignment and SPR-coupled
multichannel electrons transfer in Au-Pt@CdS heterostructures. (b) Photocurrent
density versus time (I-t) curves, (c) electrochemical impedance spectroscopy (EIS)
Nyquist plots and (d) Mott-Schottky plots of CdS and metal-CdS hybrids under Vis-NIR
light (λ > 420 nm) irradiation. (e) Linear sweep voltammetry (LSV) curves of CdS and
metal-CdS electrodes.
46, 57
and separation of electron-hole pairs in CdS.45,
Subsequently, the photogenerated electrons transfer from the
conduction band (CB) of CdS to the component of anisotropic
Au-Pt bimetal. The protons (H+) diffuse through the loose and
porous CdS thin layer and react with electrons to generate
H2.35, 58, 59 The holes retained in the valence band (VB) of CdS
by the results of electric field simulation (Fig. 3c) and TA
characterization (Fig. 3e).24, 25
can selectively oxidize alcohols to aldehydes, which is the
Electrochemical impedance spectroscopy (EIS, Fig. 4c) and
Mott-Schottky (Fig. 4d) analysis were conducted under Vis-NIR
light illumination. The arc at middle frequencies of Nyquist plot
in Fig. 4c is characteristic of charge transportation resistance.63
Apparently, the diameter of the arc for the Au-Pt@CdS
electrode is much smaller than that of CdS, Au@CdS and
Au@Pt@CdS, indicating that the resistance of interfacial
charge transportation is significantly decreased over Au-
Pt@CdS electrode. The Mott-Schottky analysis can be used to
provide fundamental insights into the charge carriers density
(ND), which is obtained from the following equation:63, 64
60
overall activity-limiting step in the redox cycle.44,
The
photogenerated electrons and holes are spatially separated,
significantly reducing the recombination probability, which
lead to greatly improved photoactivity of Au-Pt@CdS.
The investigation of photoelectrochemical (PEC) process can
further reveal the picture of electron transfer and the
underlying photoactivity enhancement mechanism. As shown
in Fig. 4b, transient photocurrent responses of different
samples under chopped Vis-NIR light illumination indicate that
the construction of bimetal-semiconductor hybrids is
conducive to enhancing the photocurrent of semiconductor
CdS, which follows the same order as the photoactivity: Au-
Pt@CdS > Au@Pt@CdS > Au@CdS > CdS. This result indicates a
more effective separation of electron-hole pairs over Au-
Pt@CdS than other electrode samples.9, 35, 61, 62 The Au-Pt@CdS
and Au@Pt@CdS consist of the same hetero-components, but
the anisotropic Au-Pt@CdS exhibits higher photocurrent and
photoactivity than isotropic Au@Pt@CdS under Vis-NIR light
illumination. This suggests that the inappropriate arrangement
of plasmonic-nonplasmonic bimetal heterostructure in
Au@Pt@CdS leads to the suppression of electric field
enhancement and electrons sink effect, as respectively proved
(
)
)
(
Where, C is the capacitance, e is the elementary electronic
charge, ε0 is the permittivity in vacuum, and ε is the dielectric
constant, specifically 8.99 for CdS.63-65 From the slope in the
plot of 1/C2 vs. V in Fig. 4d, ND can be determined by the above
equation. A summary of ND values is given in Table S3. The plot
of Au-Pt@CdS electrode shows the smallest slope value among
the samples, indicating a much higher ND than that of CdS,
Au@CdS and Au@Pt@CdS. The higher ND signifies the lower
resistance, faster charge transfer rate and consequently the
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enhanced PEC and photocatalytic performance. In addition, all 37 wt%) and benzotrifluoride (C7H5F3, BTF) were purchased
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plots show the positive slopes, indicating the n-type from Sigma Aldrich. Benzyl alcohol (C7H8O, BA), benzaldehyde
semiconductor characteristic of CdS.63, 66 The formed multiple (C7H6O, BAD) and sodium oleate (C18H33O2Na, NaOL) were
Schottky barrier between n-type CdS semiconductor and Au-Pt purchased from Aladding. 4-Methylbenzyl alcohol (C8H10O), 4-
bimetal would prevent the electrons from the metal drifting methoxybenzyl alcohol (C8H10O2), 4-chlorobenzyl alcohol
back to the semiconductor.67 Based on above results, it can be (C7H7ClO), and 4-hydroxybenzyl alcohol (C7H8O2) were supplied
concluded that Au-Pt can effectively facilitate the generation by Alfa Aesar. Cadmium acetate (C4H6O4Cd, Cd(Ac)2),
and transfer of charge carriers from CdS, due to the boosted thioacetamide (C2H5SN, TAA), chloroauric acid tetrahydrate
local electric field and the enriched spatial charge transfer (HAuCl4·4H2O), glycine acid (C2H5NO2, Gly), anhydrous ethanol
channels. Fig. 4e displays the linear sweep voltammetry (LSV) (C2H5OH, EtOH) and chloroplatinic acid hexahydrate
curves of Au-Pt@CdS, Au@Pt@CdS, Au@CdS and CdS (H2PtCl6·6H2O) were obtained from Sinopharm Chemical
electrode without light irradiation, from which it is seen that Reagent Co., Ltd. (Shanghai, China). Deionized water used in
the addition of nonplasmonic Pt into Au@CdS can obviously the synthesis was obtained from local sources.
enhance the cathodic current density and decrease the
Synthesis of Au NRs
overpotential of H2 production, thus further promoting
catalytic efficiency.31, 48
The Au NRs were prepared using a seed-mediated growth
method.68 The seed solution for Au NRs growth was prepared
as follows: 5 mL of 0.5 mM HAuCl4 was mixed with 5 mL of 0.2
M CTAB solution in a 20 mL scintillation vial. 0.6 mL of fresh
0.01 M NaBH4 was diluted to 1 mL with water and was then
injected to the above solution under vigorous stirring (1200
rpm). The solution color changed from yellow to brownish
yellow and the stirring was stopped after 2 min. The seed
solution was aged at room temperature for 2 h before use.
Subsequently, 1.4 g of CTAB and 0.25 g of NaOL were dissolved
in 50 mL of warm water (~50 °C) in a 100 mL Erlenmeyer flask.
The solution was allowed to cool down to 30 °C and 3.6 mL 4
mM AgNO3 solution. The mixture was kept undisturbed at
30 °C for 15 min after which 50 mL of 1 mM HAuCl4 solution
was added. The solution became colorless after 90 min of
stirring (700 rpm) and 0.3 mL of HCl (37 wt% in water, 12.1 M)
was then introduced. After another 15 min of slow stirring at
400 rpm, 0.25 mL of 0.064 M AA was added and the solution
was vigorously stirred for 30 s. Finally, 0.4 mL of seed solution
was injected into the growth solution. The resultant mixture
was stirred for 30 s and left undisturbed at 30 °C for 12 h for
NRs growth.
Conclusions
In summary, we have accomplished a controllable design of
bimetal-semiconductor hybrids for optimizing the redox
photocatalysis performance of alcohol conversion to H2 and
value-added aldehyde for the first time. Experimental results
and theoretical analyses indicate that the composition and
spatial configurations of metal components have significant
influences on photoabsorption, local electric field distribution
and photoinduced charge carriers transfer rate in bimetal-
semiconductor heterostructures. Compared with blank CdS
and other metal-CdS composites, the Au-Pt@CdS exhibits the
collective advantages for photoredox catalysis as follows. 1)
The unique SPR of Au NRs improves light absorption and
induces local electric field enhancement, which can promote
the charge carriers generation/migration of CdS. 2) Pt NPs
anisotropically located at the tips of Au NRs serve as electrons
reservoir and co-catalyst to steer the directional charge flow
and facilitate the proton reduction. 3) The intimate and
multiple
metal-metal
and
metal-semiconductor
heterointerfaces ensures the spatially regulated multichannel
electrons transfer and maximized plasmon-exciton interactions.
Mechanistic studies demonstrated that the photoactivity of
Au-Pt@CdS is driven by the photogenerated charge carriers
from semiconductor CdS instead of plasmonic Au-Pt bimetal. It
is hoped that this facile strategy for controllable synthesis of
bimetal-semiconductor hybrids, as well as the underlying SPR-
coupled multichannel electron transfer mechanism illustrated
here, could be instructive for further rational design of
plasmonic bimetal- or multimetal-semiconductor hybrids
toward efficient redox catalysis.
Preparation of Au-Pt
Au-Pt were prepared by using Au NRs as template.24 Briefly, 10
mL of the prepared Au NRs were separated from excess CTAB
by centrifugation twice (at 10000 rpm) and redispersed in 0.1
M CTAB solution. Then, 0.568 mL of 0.1 M ascorbic acid was
added into 10 mL of as-made Au NRs suspension. 100 μL of
0.01 M H2PtCl6·6H2O and subsequently 0.08 mL of 0.01 M HCl
were added to the reaction mixture. The mixture was left
undisturbed for 24 h at 30 °C. Pt-covered Au NRs (Au@Pt)
were prepared by using Au NRs in 0.03 M CTAB solution as
template following the same procedure.
Preparation of Au-Pt@CdS
Experimental sections
For the synthesis of Au-Pt@CdS, 10 mL of the as-prepared Au-
Pt seeds and 10 mL of aqueous Gly solution (0.2 M) were
mixed in a 50 mL vial, and subsequently 300 μL aqueous NaOH
solution (2 M) were added to the reaction mixture. The
mixture was kept at 30 °C for 30 min without stirring. Next,
200 μL of Cd(Ac)2 (0.1 M) and TAA (0.1 M) solution were
Chemicals and materials
All chemicals were analytical grade and used without further
purification.
Hexadecyltrimethylammonium
bromide
(C19H42NBr, CTAB), silver nitrate (AgNO3), sodium borohydride
(NaBH4), L-ascorbic Acid (C6H8O6, AA), hydrochloric acid (HCl,
6 | J. Name., 2012, 00, 1-3
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injected into the above solution drop by drop. The reaction tape. 5 mg of the sample was dispersed in 0.5 mL of N,N-
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was allowed to proceed at 85 °C under vigorously stirring for 2 dimethylformamide (DMF, supplied by DSOinI:o1p0.h10a3r9m/C8CShCe0m58i1c3aJl
h. The suspensions were centrifuged at 12 000 rpm for 10 min Reagent Co., Ltd.) by sonication to get slurry. The slurry (20 μL)
and washed with ethanol for three times, and then the was spread onto the pre-treated ITO glass. After air drying, the
precipitations were vacuum dried at 40 °C. Au@CdS, working electrode was further dried at 393 K for 2 h to
Au@Pt@CdS and blank CdS were also synthesized by the improve adhesion. Then, the Scotch tape was unstuck, and the
above method, except using the corresponding seeds or blank uncoated part of the electrode was isolated with epoxy resin.
CTAB (0.1 M) aqueous solution instead of Au-Pt, respectively, The exposed area of the working electrode was 0.25 cm2. The
in the synthesis process. Au-Pt/CdS sample was prepared by light irradiation source was a 300 W Xe arc lamp system
mixing the blank CdS with an appropriate amount of Au-Pt in equipped with a filter to cut off light of wavelength λ < 420 nm.
solution with vigorous stirring for 24 h followed by the wash The cathodic polarization curves were obtained using the
and dry process similar to Au-Pt@CdS.
linear sweep voltammetry (LSV) technique with a scan rate of
2 mV s-1. The electrochemical impedance spectroscopy (EIS)
Material characterization
experiments were conducted on
a
AUTOLAB M204
The crystal phase properties of the samples were analysed workstation.
with a Bruker D8 Advance X-ray diffractometer (XRD) using Ni-
FDTD simulations
filtered Cu Kα radiation at 40 kV and 40 mA in the 2θ ranging
from 20° to 80° with a scan rate of 0.02° per second. The The electric field simulations were carried out by using finite-
optical properties of the samples were characterized using the difference time-domain (FDTD) software package (Lumerical
Cary-5000 ultraviolet-visible-near infrared diffuse reflectance Solutions, Inc.). The refractive indices of CdS, BTF, Au and Pt
23, 69
spectrophotometer (DRS, Varian Co.). The morphology and were taken from previous reported data.19,
A total-
elemental distribution of the samples were analysed by field- field/scattered field (TFSF) source was used as an incident field
emission scanning electron microscopy (FESEM) on a FEI Nova into the simulation region, which coincided with wavelength of
NANOSEM 230 spectrophotometer and transmission electron our experimental irradiation source. Perfectly matched layers
microscopy (TEM), high-resolution TEM (HRTEM) and elements (PML) boundary conditions were used in our simulations. The
mapping analysis using a JEOL 2100F instrument at an Au NRs are a cylinder with round ends and the size was taken
accelerating voltage of 200 kV. Raman spectroscopy was to match their average values. The radius of the cylinder is
performed on a Renishaw inVia Raman System 1000 with a 14.5 nm and radii of the ends are 8 nm. The total length of the
532 nm Nd:YAG excitation source at room temperature. X-ray Au NRs is 92.5 nm. All the CdS shell thickness is 20 nm. For the
photoelectron spectroscopy (XPS) measurements were model of Au-Pt@CdS, ellipse Pt spheres with diameters of 14
performed using
a
Thermo Scientific ESCA Lab250 nm were located at both ends of the Au NRs with a total length
spectrometer that consists of a monochromatic Al Kα as the X- of 98 nm. For Au@Pt@CdS, the Pt shell is a cylinder with
ray source, a hemispherical analyser, and a sample stage with radius of 2.1 nm and total length of the Au NRs is 107.9 nm.
multiaxial adjustability to obtain the composition on the
Photoactivity
surface of samples. All of the binding energies were calibrated
by the C 1s peak of the surface adventitious carbon at 284.6 eV. The experiments were performed referring to previously
The elemental concentrations analysis was performed by an reported literatures with some modifications.44, 70 In a typical
inductively coupled plasma emission spectroscopy instrument photocatalytic reaction, 2 mL catalyst suspension (1 mg mL-1 in
(ICP, PerkinElmer Optima 8000). The carriers dynamic were BTF) containing 0.5 M alcohols was placed in a quartz reactor
measured by using femtosecond transient absorption (25 mL) equipped with a magnetic stir bar. The reaction
spectroscopy (Time-Tech Spectra, femtoTA-100). Part of the suspension was sonicated for 2 min at room temperature and
800 nm output pulse from the amplifier was used to pump a purged with Ar gas for 30 min. The reactor was then tightly
TOPAS Optical Parametric Amplifier (OPA) which generates the sealed and then stirred for 30 minutes in the dark to achieve
370 nm pump beam. The pump pulses were chopped by a an adsorption-desorption equilibrium. A 300 W Xe arc lamp
synchronized chopper at 500 Hz and the absorbance change (PLS-SXE 300, Beijing Perfect light Co., Ltd.) with a filter to cut
was calculated with two adjacent probe pulses (pump-blocked off light of wavelength λ < 420 nm was used as the irradiation
and pump-unblocked), and the pump power was source. The light intensity was fixed at 800 mW cm-2. The
approximately 1 uW. The samples were dispersed in water for photon flux of incident light was measured using an Optical
all pump-probe characterizations performed under ambient Power/Energy Meter (Newport 842-PE). The irradiation area is
conditions. The photoelectrochemical analysis was carried out 3.8 cm2. During photocatalysis, the suspension was
in a conventional three-electrode cell using a Pt plate and an continuously stirred to ensure uniform irradiation. The evolved
Ag/AgCl electrode as the counter electrode and reference gases were analysed by gas chromatograph (Shimadzu GC-
electrode, respectively. The electrolyte was 0.2 M Na2SO4 2014C, MS-5 A column, Ar carrier) equipped with a thermal
aqueous solution containing 0.1 mM BA. The working conductivity detector (TCD). Products in solution were
electrode was prepared on indium-tin oxide (ITO) glass that quantified by Agilent Gas Chromatograph (GC-7820) with
was cleaned by sonication in ethanol for 30 min and dried at flame-ionization detector (FID) and identified by gas
353 K. The boundary of ITO glass was protected using Scotch chromatography-mass
spectrometry
(GC-MS,
Agilent
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Journal Name
Technologies, GC6890N, MS 5973). The recycling test for
photocatalytic conversion of BA over Au-Pt@CdS was
performed as follows. After 5 h reaction under Vis-NIR light
irradiation, the suspension was centrifuged and mixed with 2
mL BTF containing 0.5 M BA for continuous test. Conversion of
BA and selectivity for BAD were calculated with following
equations:71
7
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M.-Q. Yang, M. Gao, M. Hong and G. W. Ho, Adv.
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J. Chen, X.-J. Wu, L. Yin, B. Li, X. Hong, Z. Fan, B. Chen, C.
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(
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(
)
Here C0 is the initial concentration of BA; CBA and CBAD are the
concentrations of the residual BA and the corresponding BAD
at a certain time after the catalytic reaction, respectively. The
apparent quantum efficiency (AQE) was calculated from the
ratio of twice the number of H2 molecules to the number of
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photoreaction time and
λ is the wavelength of the
monochromatic light. The power density of different
19
20
21
monochromatic light was fixed at 30.0 mW·cm-2.
Acknowledgements
The support from the National Natural Science Foundation of
China (NSFC) (21872029, U1463204, 21173045), the Award
Program for Minjiang Scholar Professorship, the Natural
Science Foundation (NSF) of Fujian Province for Distinguished
Young Investigator Rolling Grant (2017J07002), the
Independent Research Project of State Key Laboratory of
Photocatalysis on Energy and Environment (NO. 2014A05), and
the 1st Program of Fujian Province for Top Creative Young
Talents is gratefully acknowledged.
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DOI: 10.1039/C8SC05813J
An anisotropic bimetal-semiconductor heterostructure with efficient charge carriers generation, transfer and utilization for
plasmon-enhanced photoredox catalysis.
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