Article

Cite This: J. Am. Chem. Soc. 2019, 141, 13434−13441 pubs.acs.org/JACS

In Situ Construction of a Cs2SnI6 Perovskite Nanocrystal/SnS2

Nanosheet Heterojunction with Boosted Interfacial Charge Transfer
Xu-Dong Wang, Yu-Hua Huang, Jin-Feng Liao, Yong Jiang, Lei Zhou, Xiao-Yan Zhang,
Hong-Yan Chen, and Dai-Bin Kuang*
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun
Yat-sen University, Guangzhou 510275, P. R. China
*
S Supporting Information
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ABSTRACT: Heterojunction engineering has played an indispensable role

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in the exploitation of innovative artificial materials with exceptional

properties and has consequently triggered a new revolution in achieving
high-performance optoelectronic devices. Herein, an intriguing halide
perovskite (PVK) and metal dichalcogenide (MD) heterojunction, i.e., a
lead-free Cs2SnI6 perovskite nanocrystal/SnS2 nanosheet hybrid, was
fabricated in situ for the first time. Comprehensive investigations with
experimental characterizations and theoretical calculations demonstrate that
cosharing of the Sn atom enables intimate contact in the Cs2SnI6/SnS2
hybrid together with a type II band alignment structure. Additionally,
ultrafast carrier separation between SnS2 and Cs2SnI6 has been observed in
the Cs2SnI6/SnS2 hybrid by transient absorption measurements, which
efficiently prolongs the lifetime of the photogenerated electrons in SnS2
(from 1290 to 3080 ps). The resultant spatial charge separation in the
Cs2SnI6/SnS2 hybrid evidenced by Kelvin probe force microscopy (KPFM) significantly boosts the photocatalytic activity
toward CO2 reduction and the photoelectrochemical performance, with 5.4-fold and 10.6-fold enhancements compared with
unadorned SnS2. This work provides a facile and effective method for the in situ preparation of PVK-MD heterojunctions,
which may significantly stimulate the synthesis of various perovskite-based hybrid materials and their further optoelectronic
applications.

■ INTRODUCTION
Halide perovskites (PVKs) and metal dichalcogenides (MDs)
are currently striking semiconductor materials that have
aroused tremendous scientific interest because of their
impressive optoelectronic properties, which further allow for
their successful application in solar cells,1 photodetectors,2
LEDs,3 photocatalysts,4,5 etc. Specifically, PVKs have been
highlighted as having a high absorption coefficient, a suitable
band gap, and excellent charge carrier transport, and as a
consequence, the record power conversion efficiency (PCE) of
perovskite solar cells has recently risen to 25.2%.6 MDs (such
as MoS2 and WS2) are generally characterized by a unique 2D
semiconducting structure accompanied by excellent photo-
electric properties.7 However, the severe charge recombination
in a single MD will result in inferior photon conversion
efficiency because the bulk recombination process is much
faster than the interfacial charge transfer process, which
severely restricts the application of MDs in optoelectronic
devices.
To solve this obstacle, interfacing MDs with another
material to construct a heterojunction is a simple but effective
method. Exquisitely tailoring and optimizing the energy band
alignment in the hybrid can provide a driving force for
boosting the interfacial electron−hole separation efficiency and
suppressing recombination.8−10 To this end, PVKs have been
regarded as first-rate candidates considering their superior
charge transport behavior. Accordingly, the fabrication of PVK-
MD hybrid structures, such as MAPbI3/WSe2,11 MAPbI3/
MoS2,12,13 and CsPbBr3/WS2,14 has been continuously
reported. Benefiting from the merits of PVKs, the afore-
mentioned PVK-MD hybrids are endowed with enhanced light
absorption as well as optimized charge carrier dynamics, which
further translate into improved performance in photodetector
applications.
Generally, a high-quality interface is highly desirable in
heterojunctions for the efficient separation of the electron−
hole pairs both timely and spatially.15 Sharing of a
corresponding metal by the two materials in the hybrid
heterogeneous complex can effectively prolong the charge
carrier lifetime and increase the carrier density.16−21
Unfortunately, the currently reported PVK-MD hybrids were
fabricated via conventional physical mixing or stepwise
deposition methods, which are not favorable for the formation
of a close-contact interface. Additionally, the toxicity of lead in
perovskites remains a concern hindering their large-scale
Received: April 25, 2019
Published: August 5, 2019

© 2019 American Chemical Society 13434 DOI: 10.1021/jacs.9b04482

J. Am. Chem. Soc. 2019, 141, 13434−13441
Journal of the American Chemical Society
implementation.22,23 In the search for lead-free perovskite
materials, Sn-based perovskites have shown a lower optical
band gap (Eg) compared with the Pb analogs.24−28 In
particular, all-inorganic Cs2SnI6 is preferred considering its
robust chemical stability and outstanding conductivity. For
instance, Cs2SnI6 thin films possess a high hole mobility of 3.82
× 102 cm2 V−1 s−1,29 higher than that of MAPbBr3 and Si
single crystals.30−33 Benefiting from the superior hole mobility,
Cs2SnI6 has been widely utilized as a hole transport material in
solar cells.29,34,35
In this work, an elaborately designed PVK-MD hetero-
structure, i.e., a 0D Cs2SnI6 nanocrystal/2D SnS2 nanosheet
hybrid, was synthesized by simply stirring as-prepared SnS2
nanosheets in a CsI precursor solution. A comprehensive
investigation involving experiments and theoretical calculations
revealed that a type II band alignment was formed in the
hybrid, and more importantly, an atomic-level close-contact
interface was fostered by cosharing of the Sn atoms.
Additionally, transient absorption (TA) and Kelvin probe
force microscopy (KPFM) results indicated ultrafast hole
transfer behavior in the hybrid from SnS2 to Cs2SnI6. As a
consequence, a prolonged photogenerated electron lifetime
was observed in SnS2 (from 1290 to 3080 ps) owing to the
significantly restrained electron−hole pair recombination.
Accordingly, 5.4- and 10.6-fold enhancements were achieved
in visible photocatalytic CO2 reduction and photoelectrochem-
ical measurements for the Cs2SnI6/SnS2 hybrid compared with
the unadorned SnS2, which can be attributed to the improved
light absorption and boosted charge separation efficacy after
incorporation of Cs2SnI6.
■
EXPERIMENTAL SECTION
Materials. CsI (99.0%), thioacetamide (99.0%), hydroiodic acid
(55.0∼58.0%), hypophosphorous acid (A.R.), Sn (99.99%), trietha-
nolamine, and benzoquinone were purchased from Aladdin Industrial
Corporation. SnCl4 (A.R.) was purchased from Sinopharm Group
Chemical Reagent Co., Ltd. EtOH (A.R.) and diethyl ether (A.R.)
were provided by Guangzhou Chemical Reagent Factory.
Synthesis of SnS 2 Nanosheets. The synthesis of SnS 2
nanosheets was based on a modified traditional hydrothermal
process.36 First, a precursor solution was prepared by gradually
adding SnCl4 (20 mmol) into ethanol solution (100 mL) with
thioacetamide (60 mmol) under stirring. After the complete
dissolution of SnCl4, the solution was loaded into reaction kettles
and maintained at 70 °C for 6 h. After cooling to room temperature,
the precipitate was obtained by centrifugation at 8000 rpm.
Subsequently, the product was washed with water and ethanol before
drying in vacuum.
Synthesis of the Cs2SnI6/SnS2 Hybrid. As-prepared SnS2 (1.0
mmol, 0.2012 g) was added to a mixed solution of EtOH (5 mL) and
HI (5 mL) with different dissolved CsI contents (0, 0.01, 0.02, and
0.04 mmol). Notably, 2−3 drops of H3PO2 were added to prevent HI
from oxidizing. The mixture solution was stirred in an ice bath for 30
min for the in situ construction of Cs2SnI6 nanocrystals on SnS2
nanosheets. The product was collected by centrifugation at 10000
rpm and then washed with ether 3 times before drying.
Characterizations. X-ray diffraction (XRD) data were acquired
on an X-ray powder diffractometer (Rigaku MiniFle X600). The
morphology was characterized by field emission scanning electron
microscopy (SEM, Gemini 500) and transmission electron micros-
copy (TEM, FEI Tecnai G2 F30). Absorption and photo-
luminescence spectra were obtained using an ultraviolet−visible−
near-infrared spectrophotometer (Shimadzu UV-3600) and a
fluorescence spectrophotometer (Edinburgh FLS980), respectively.
X-ray photoelectron spectroscopy (XPS) measurements were
performed on an ESCALAB 250 (Thermo Fisher Scientific). KPFM
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characterization was performed under ambient conditions using a
Bruker Dimension Fastscan.
TA spectroscopy Characterizations. TA spectra of SnS2 and
Cs2SnI6/SnS2 were measured on a Helios femtosecond transient
absorption spectrometer (Ultrafast Systems, LLC). A 375 nm pump
pulse was generated via an optical parametric amplifier (OPerA Solo,
Coherent) from the original laser with a wavelength of 800 nm (100
fs, 1 kHz repetition rate, Astrella-Tunable-V-F-1k, Coherent). A broad
white light continuum probe spectrum was generated in a sapphire
crystal.
Photocatalytic Measurements. Photocatalytic CO2 reduction
experiments were performed in a 60 mL sealed quartz glass cell filled
with high purity CO2 at a partial pressure of 1 atm. Then, 5 μL of
H2O and 5 μL of CH3OH were injected into the reactor. Xenon light
(150 mW cm−2, 400 nm filter, Newport LCS-100) was used as the
light source. The generated products were analyzed by gas
chromatography (GC9790 plus, Fuli Analytical Instrument Co.,
Ltd.). The CO2 reaction activity in the photocatalysis was quantified
by the CH4 production yield: CH4 yield = CH4 production (mol)/
quality of catalyst (g).
Photoelectrochemical Measurements. Photoelectrochemical
experiments were performed in a three-electrode electrochemical
quartz glass cell with a dichloromethane solution of 0.1 M ammonium
hexafluorophosphate as the electrolyte. A SnS2 or Cs2SnI6/SnS2 thin
film was deposited on FTO as the working electrode, and Ag/AgCl
(saturated KCl) and Pt mesh were used as the reference electrode and
the counter electrode, respectively. Xenon light (150 mW cm−2, 400
nm filter, Newport LCS-100) was used as the light source. Light
chopping equipment (PFS40A, Beijing Perfect Light Technology Co.,
Ltd.) was used to control the light on/off.
Density Functional Theory (DFT) Calculations. DFT calcu-
lations were performed using the CP2K package.37 The PBE
functional38 was used to describe the system by Grimme’s D3
correction.39 Unrestricted Kohn−Sham DFT has been used as an
electronic structure method in the framework of the Gaussian and
plane wave methods.40,41 The Goedecker−Teter−Hutter (GTH)
pseudopotentials42,43 and DZVP- MOLOPT-GTH basis sets40 were
employed to describe the molecules along with a plane-wave energy
cutoff of 500 Ry. Geometry optimizations were conducted based on
PBE+D3. The correct electronic structures of Cs2SnI6, SnS2, and the
Cs2SnI6/SnS2 heterojunction were obtained from the Heyd−
Scuseria−Ernzerhof (HSE06) hybrid functional.44,45 In the HSE06
functional, the exchange-correlation energy is defined as
HSE
E XC = αE XSR (ω) + (1 − α)E XPBE,SR (ω) + E XPBE,LR (μ) + ECPBE
(1)
where the Coulomb interaction is composed of short-range (SR) and
long-range (LR) parts, and ω is the screening factor of 0.11 au (0.20
Å−1). To fit the experimental band gap, the fraction of HF exchange is
set to 0.25 for SnS2 and 0.33 for Cs2SnI6. Because of the high cost of
the standard hybrid functional, the Auxiliary Density Matrix Method
(ADMM) was utilized. Specifically, the cFIT-11 basis set was selected
for Cs, along with cFIT7 for I, cFIT3 for S, and cFIT7 for Sn. The
work function (Φ) of a material commonly serves as an intrinsic
reference for band alignment, where that of vacuum is set as 0. The
work function is determined by the energy of the electrostatic
potential in vacuum (Evac) and the Fermi level of the system (EF), as
shown in the following equation:
Φ = Evac − E F (2)
The band edge potentials of the valence band (VB) and conduction
band (CB) are calculated based on the following equations:
E VB = χ − Ee + 0.5Eg (3)
ECB = E VB − Eg (4)
The charge density difference is defined as follows:
Δρ = ρ(Cs2SnI6 /SnS2 ) − ρ(Cs2SnI6) − ρ(SnS2 ) (5)
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Scheme 1. Schematic Illustration of the Synthesis Procedure for the Cs2SnI6/SnS2 Heterostructure
Figure 1. SEM and TEM images of SnS2 (a, b); SEM, EDX elemental mapping, TEM and HRTEM images of Cs2SnI6/SnS2 (c−f).
where Δρ is the charge difference between the two substrates with
ρ(Cs2SnI6), ρ(SnS2), and ρ(Cs2SnI6/SnS2) is the total charge density
of the composite.
■ RESULTS AND DISCUSSION
Synthesis and Characterization of the Cs2SnI6/SnS2
Heterostructure. As shown in Scheme 1, the Cs2SnI6/SnS2
heterostructure was fabricated by dispersing the hydro-
thermally synthesized SnS2 nanosheets in HI/EtOH solution
containing CsI (see the Experimental Section for details).
Here, the concentration of CsI was controlled at 1.0 mM, 2.0
mM, or 4.0 mM, and the corresponding products were
denoted Cs2SnI6(0.5)/SnS2, Cs2SnI6(1.0)/SnS2, and Cs2SnI6
(2.0)/SnS2, respectively.
According to the XRD patterns (Figure S1), the hydro-
thermally synthesized SnS2 nanosheets crystallized into a
Berndite-2T layered structure. Compared with the standard
pattern (JCPDS, No. 23-0677), the (001) characteristic peak
of the SnS2 nanosheet shifts from 15.12° to 14.38°, which can
be attributed to the enlarged interlayer spacing (6.15 Å)46,47
and will probably be beneficial for the subsequent ion
intercalation. In contrast to the parental SnS2, a series of
new peaks that can be well indexed to the cubic Cs2SnI6
(JCPDS NO. 51-0466) emerge after the CsI/HI treatment,
indicating the formation of the Cs2SnI6/SnS2 hybrid. More-
over, the peak intensity of Cs2SnI6 is gradually enhanced with
increasing CsI concentration, indicating that the loading
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amount of Cs2SnI6 on SnS2 nanosheets is increased. Notably,
the vertical distance between adjacent Sn planes in Cs2SnI6
(5.83 Å) is similar to that in SnS2 (6.15 Å), corresponding to a
low mismatch factor (f) of 5.2% [f = (1 − d(Cs2SnI6)/
d(SnS2)], where d is the vertical distance between adjacent Sn
planes in the Cs2SnI6 [001]∥SnS2 [001] direction. This low
mismatch provides a reasonable condition for Cs2 SnI6
embedding in the SnS2 crystal lattice (Figure S2). As revealed
in the SEM images (Figure 1a and c), pristine SnS2 and the
Cs2SnI6/SnS2 hybrid possess similar nanosheet morphologies.
However, a much coarser surface is observed for the Cs2SnI6/
SnS2 hybrid nanosheet according to the TEM image (Figure
1e), rather than the smooth flat surface for the unadorned SnS2
nanosheet (Figure 1b). Additionally, nanocrystals with sizes of
4−10 nm are distributed on the nanosheet surface in the
Cs2SnI6/SnS2 hybrid. The distinct interplanar spacing of 0.288
nm that agrees well with the (004) plane of the Cs2SnI6
nanocrystal further verifies its high crystallinity (Figure 1f).
The distribution of the elements Cs, Sn, I, and S determined
from the energy dispersive X-ray (EDX) elemental mapping
(Figure 1d) reveals that Cs2SnI6 nanocrystals were homoge-
neously grown on the SnS2 nanosheets. Corresponding to the
aforementioned XRD results, the coverage of Cs2SnI6 nano-
crystals on SnS2 increases with increasing CsI concentration
from 1.0 mM to 2.0 mM (Figure S3 and Figure 1).
Augmenting the CsI concentration up to 4.0 mM results in
the formation of large Cs2SnI6 particles with sizes of 1−2 μm
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Figure 2. Calculated PDOS of Cs2SnI6 (a), SnS2 (b), and Cs2SnI6/SnS2 (c); charge density difference (d) and planar-averaged electron density
difference Δρ(z) (e) for Cs2SnI6/SnS2; diagram of the band edge positions of Cs2SnI6 and SnS2 (f).
(Figure S4), which probably can be ascribed to the
overaccelerated nucleation rate due to the high concentration.
To further probe the chemical interaction between Cs2SnI6
and SnS2, XPS was conducted for the Cs2SnI6/SnS2 composite,
and the results were compared with those for single Cs2SnI6
and SnS2 (Figure S5). Obviously, different binding energies of
Sn 3d5/2 and Sn 3d3/2 are found in pristine Cs2SnI6 (487.13
and 495.56 eV) and SnS2 (486.76 and 495.18 eV), which is
reasonable due to the different chemical environments of the
Sn atoms. However, the Sn 3d signals of the Cs2SnI6/SnS2
composite are not consistent with those of pristine SnS2 or
Cs2SnI6 but lie in between, closer to those of SnS2. Similarly,
the S 2p3/2 peak of Cs2SnI6/SnS2 also shifts to a higher binding
energy, from 161.67 to 161.82 eV, compared with that of SnS2.
This result is interpreted as partial replacement of S by I
causing a decrease in the electron cloud density of Sn and
further strengthening its electron accepting ability. As a result,
the electron transfer tendency from S to Sn will be intensified,
thus leading to the shift to a higher binding energy. Therefore,
the synchronous shifts in the Sn and S signals can be attributed
to the formation of S···Sn···I bonding in the Cs2SnI6/SnS2
hybrid.
The optical properties of the Cs2SnI6/SnS2 hybrid were
studied by UV−vis−NIR and photoluminescence (PL)
spectroscopy. The SnS2 nanosheet is characterized by a band
gap of approximately 2.17 eV and a distinct tail stretching to
1000 nm owing to the indirect band gap absorption (Figure
S6a). Benefiting from the absorption of Cs2SnI6, the light
absorbance in the range 600−950 nm is significantly enhanced
in the Cs2SnI6/SnS2 hybrid. In contrast, the PL intensity at
∼575 nm originating from SnS2 is dramatically quenched after
incorporation of Cs2SnI6 nanocrystals. The quenching degree
of the PL intensity is aggravated with increasing amount of
Cs2SnI6 nanocrystals (Figure S6b), implying that the photo-
generated electron−hole radiative recombination in SnS2
nanosheets is significantly restrained after the introduction of
Cs2SnI6 nanocrystals. The charge transfer behavior can be
further verified by time-resolved PL measurements (Figure S7
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and Table S1). By using a biexponential fitting, two time
components (τ1 = 2.1 ns and τ2 = 22.6 ns) are derived for
SnS2. In comparison, accelerated PL decay is exhibited in
Cs2SnI6(1.0)/SnS2, with τ1 = 1.5 ns and τ2 = 9.1 ns. According
to ultraviolet photoelectron spectroscopy (UPS) analysis
(Figure S8), a type II band alignment was formed in the
Cs2SnI6/SnS2 hybrid (Figure S9), which is beneficial for hole
extraction and transfer from SnS2 to Cs2SnI6 and accounts for
the weakened PL intensity in the Cs2SnI6/SnS2 hybrid.
DFT Calculations. DFT was further employed to
investigate the electronic structures and interfacial properties
in the Cs2SnI6/SnS2 hybrid (Figure 2). As revealed by the
calculated projected density of states (PDOS) of Cs2SnI6
(Figure 2a), the valence band maximum (VBM) is mainly
dictated by the I 5p orbital, and the conduction band
minimum (CBM) consists of the I 5p and Sn 5s states. In
the case of SnS2, the VBM consists of S 3p and Sn 4d orbitals,
and the CBM is occupied by S 3p and Sn 5s orbitals. The band
gaps calculated with the HSE06 functional of Cs2SnI6 and SnS2
are 1.12 and 2.29 eV, respectively, agreeing well with the
experimental values.16,35 Band calculations of SnS2 and Cs2SnI6
(Figure 2c) reveal that the VBM of SnS2 is higher than that of
Cs2SnI6, whereas the CBM of SnS2 is lower than that of
Cs2SnI6. As a consequence, a typical type II band alignment
formed in the Cs2SnI6/SnS2 heterojunction, which is in
accordance with the electronic band structure displayed in
the UPS results. Furthermore, the density of states at the VBM
of Cs2SnI6/SnS2 (Figure 2c) is much higher than that of single
SnS2, which is responsible for the enhanced light absorption, as
confirmed by the UV−vis−NIR spectrum. To further probe
the interfacial charge transfer in the Cs2SnI6/SnS2 hetero-
junction, the charge density difference was also investigated.
As depicted in Figure 2d and 2e, the planar-averaged charge
density difference along the Z direction for Cs2SnI6/SnS2 is
redistributed due to the formation of electron accumulation
and hole depletion as a result of the hole transfer from SnS2 to
Cs2SnI6 and electron transfer from Cs2SnI6 to SnS2.
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Figure 3. Contour plot of the TA spectra of SnS2 (a) and Cs2SnI6/SnS2 (b) in toluene. TA kinetic traces of SnS2 and Cs2SnI6/SnS2 in toluene
recorded at 525 nm (c). TA kinetic traces of SnS2 in H2O with different chemical additives (BQ as an electron scavenger and TEOA as a hole
scavenger) monitored at 525 nm (d).

Figure 4. Comparative KPFM study of SnS2 and Cs2SnI6/SnS2. AFM height images (a, d); SPV images (ΔCPD = CPDlight − CPDdark) (b, e); line
profiles of the SPV difference (c, f).

TA Spectra Measurements. Ultrafast TA spectroscopy is
regarded as a powerful technique that can enable an in-depth
study of the charge transport dynamics in semiconductors. As
shown in Figure 3, a broad positive absorption (PIA) feature
peaking at ∼525 nm is observed in both SnS2 and Cs2SnI6/
SnS2, which originated from the photogenerated electrons in
SnS2 and will be discussed later.48,49 As can be clearly
perceived in the contour plot of the TA spectra (Figure 3a and
13438
3b), much stronger PIA intensity is observed in Cs2SnI6/SnS2
compared to pristine SnS2. Additionally, the kinetic decay
curves probed at 525 nm (Figure 3c) appear much more
sluggish for the Cs2SnI6/SnS2 sample than for the single SnS2
nanosheet. Specifically, the fitted time profiles exhibit a 2.4-fold
longer delay time for Cs2SnI6/SnS2 (3080 ps) than for single
SnS2 (1290 ps). The relative intensity and the decay time of
the TA signal can be utilized to interpret the excited charge
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carrier density and the charge carrier lifetime, respectively.

Therefore, the resultant increase in the PIA intensity and
retarded decay after incorporation of Cs2SnI6 can be construed
as a prolonged lifetime of the photogenerated electrons.
To verify the positive role of the heterojunction structure in
the resultant prolonged electron lifetime, the TA spectra of
SnS2 were further collected in the presence of a hole scavenger
(triethanolamine, TEOA)50 or an electron scavenger (benzo-
quinone, BQ).51 The PIA signal intensity of SnS2 increases
after the introduction of TEOA (Figure S10a and S10b),
whereas it decreases in the presence of BQ (Figure S10c).
Additionally, the decay kinetics of the signal at 525 nm (Figure
3d, Table S2) show that the decay is accelerated in the
presence of BQ and retarded with TEOA addition. Therefore,
the observed PIA signal in the TA spectra of the Cs2SnI6/SnS2
hybrid can be concluded to originate from the photogenerated
electrons. Based on the charge dynamics analysis and band
calculations, two factors contribute to the increased electron
lifetime of Cs2SnI6/SnS2. One factor is that photogenerated
holes in SnS2 can be efficiently extracted out to Cs2SnI6, similar
to TEOA; thus, the internal electron−hole recombination in
SnS2 is efficiently suppressed. The other factor is that the type
II band alignment between Cs2SnI6 and SnS2 is beneficial for
the electron injection from Cs2SnI6 to SnS2.
KPFM Measurements. To further corroborate the
aforementioned charge separation/transfer process in
Cs2SnI6/SnS2, KPFM was performed to directly observe the
spatial charge distribution. The AFM height mapping images
(Figure 4a, d) demonstrate that the parental SnS2 and the
Cs2SnI6/SnS2 hybrid possess nanosheet morphologies. The
KPFM images and the corresponding line profiles of the
surface photovoltage (SPV) difference are displayed in Figure
4b−c, e−f. No significant SPV signals are observed in the Figure 5. Comparison of photocatalytic CO2 reduction activities of
parental SnS2 nanosheet due to the rapid charge carrier SnS2, Cs2SnI6(0.5)/SnS2, Cs2SnI6(1.0)/SnS2, and Cs2SnI6(2.0)/SnS2
recombination. In contrast, a distinct positive SPV is observed (a); schematic illustration of the photocatalytic CO2 reduction (b).
in Cs2SnI6/SnS2.The positive SPV signals arise from the
surviving holes accumulating on the surface of Cs2SnI6 after
illumination. The difference in the positive and negative g−1) compared to the pristine SnS2 sample (1.12 μmol g−1).
potentials of Cs2SnI6/SnS2 is approximately 49.2 mV, which is Excess Cs2SnI6 is not conducive to the further improvement of
evidently higher than that of SnS2 (25.9 mV). Such a the photocatalytic performance. Based on the above UV−vis−
remarkable difference in SPV signals between the SnS2 and NIR, PL, TA, KPFM, and DFT results, the underlying
Cs2SnI6/SnS2 samples strongly verifies the existence of spatial mechanism of the boosted catalytic performance observed in
charge accumulation/depletion at the interfaces in the the Cs2SnI6/SnS2 sample is mainly rooted in two aspects. In
Cs2SnI6/SnS2 hybrid. situ construction of Cs2 SnI6 nanocrystals on the SnS2
Photocatalytic CO2 Reduction. Efficient charge carrier nanosheet enhances the light absorption capability in the
separation and transfer are of critical importance in the range 600−950 nm, thus increasing the carrier concentration
evaluation of a high-performance photocatalyst. Therefore, as a of the photocatalyst. Additionally, Cs2SnI6 embedding in the
proof-of-concept application, we applied SnS2 and Cs2SnI6/ SnS2 crystal lattice gives rise to an intimate contact interface in
SnS2 as photocatalysts for CO2 reduction. The product yield is the Cs2SnI6/SnS2 type II heterojunction (Figure 5b), which
plotted in Figure 5a as a function of the Cs2SnI6 loading significantly promotes charge separation and further suppresses
amount. Apparently, the product of the CO2 photocatalytic electron−hole recombination. The operating stability of
reduction is CH4,52 and the Cs2SnI6 content plays a significant Cs2SnI6(1.0)/SnS2 under the CO2 photocatalytic reaction
role in the final morphology and thus in the photocatalytic conditions was also investigated. No obvious decline in CH4
performance of the Cs2SnI6/SnS2 hybrid. Notably, incorpo- evolution is observed after 3 cycles of 3 h repeated
ration of Cs2SnI6 unquestionably boosts the catalytic activity of experiments, indicating that Cs2SnI6(1.0)/SnS2 has good
SnS2 due to the facilitated charge separation. However, the catalytic stability (Figure S11). In addition, neither structural
particle size of Cs2SnI6 nanocrystals on SnS2 increases from 4 transformation nor absorption behavior changes are found in
to 10 nm to 1−2 μm with increasing CsI concentration from the XRD pattern (Figure S12a) and UV−vis−NIR spectra
2.0 mM to 4.0 mM (Figure 1 and Figure S4), which is (Figure S12b) of Cs2SnI6(1.0)/SnS2 after photocatalytic
speculated to trigger severe charge carrier recombination in the reaction. The chemical stability of the Cs2SnI6/SnS2 hybrid
large Cs2SnI6 particles and thus hinder the electron transfer after the photocatalytic measurement was also detected by XPS
from Cs2SnI6 to SnS2. After optimization, a 5.4-fold enhance- (Figure S13), showing signals nearly identical to those of the
ment is achieved in the Cs2SnI6(1.0)/SnS2 sample (6.09 μmol fresh counterpart. These results suggest that Cs2SnI6(1.0)/
13439 DOI: 10.1021/jacs.9b04482
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SnS2 possesses good stability during photocatalytic CO2
reduction.
Photoelectrochemical Measurements. The photoelec-
trochemical (PEC) performances of Cs2SnI6/SnS2 and SnS2
were further measured by constructing a PEC cell to reveal the
charge carrier separation and transfer behavior in the Cs2SnI6/
SnS2 hybrid. The trends of the PEC performance (Figure S14)
are in good agreement with the CO2 reduction photocatalytic
activity results. The highest photocurrent density is observed
for the Cs2SnI6(1.0)/SnS2 photoelectrode, approximately 36
μA cm−2, which is 10.6 times higher than that for pristine SnS2
(∼3.4 μA cm−2). As mentioned above, excessive Cs2SnI6
loading will give rise to large particles, which are not favorable
for the improvement of the PEC performance.
■
CONCLUSION
In summary, a novel Sn atom cosharing Cs2SnI6 perovskite
nanocrystal/SnS2 nanosheet heterojunction was synthesized in
situ via a facile solution method for the first time. A combined
investigation with DFT calculations as well as TA and KPFM
characterizations demonstrated a type II Cs2SnI6/SnS2 hybrid
possessing an intimate contact interface, which can effectively
promote photoexcited charge carrier transfer, namely, holes
from SnS2 to Cs2SnI6 and electrons from Cs2SnI6 to SnS2. As a
proof-of-concept application, photocatalytic CO2 reduction
and PEC experiments further verified that the accumulated
electrons in SnS2 with an efficiently prolonged lifetime boosted
the performance 5.4-fold and 10.6-fold. We believe that the
current in situ construction of heterojunctions by an atom
cosharing strategy will stimulate the synthesis of various
perovskites-MDs (Cs3M2X9/M2Y3, M = Bi, Sb, X = Br, I and Y
= S, Se) and widen the application scope in electronics, solar
cells, photodetectors, and photocatalysts.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.9b04482.
Additional experimental details, XRD patterns, UV−vis-
NIR spectra, PL and XPS characterizations of SnS2 and
Cs2SnI6/SnS2, TA spectra of SnS2, SEM images of
Cs2SnI6/SnS2, UPS spectra of Cs2SnI6 and SnS2,
Recycled photocatalytic measurements of Cs2SnI6/SnS2
and PEC measurements of SnS2 and Cs2SnI6/SnS2
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*kuangdb@mail.sysu.edu.cn (D.B.K.)
ORCID
Hong-Yan Chen: 0000-0001-6704-1665
Dai-Bin Kuang: 0000-0001-6773-2319
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the financial support from the
National Natural Science Foundation of China (21875288,
21802172), the GDUPS (2016), the NSF of Guangdong
Province (2018A030313009), and the Fundamental Research
Funds for the Central Universities.
13440
Article
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