ARTICLE

Received 5 Jul 2016 | Accepted 9 Dec 2016 | Published 1 Feb 2017 DOI: 10.1038/ncomms14224 OPEN

Self-surface charge exfoliation and electrostatically

coordinated 2D hetero-layered hybrids
Min-Quan Yang1, Yi-Jun Xu2,3, Wanheng Lu4, Kaiyang Zeng4, Hai Zhu5, Qing-Hua Xu5 & Ghim Wei Ho1

At present, the technological groundwork of atomically thin two-dimensional (2D)

hetero-layered structures realized by successive thin film epitaxial growth is in principle
constrained by lattice matching prerequisite as well as low yield and expensive production.
Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly
scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically,
bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a
surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a
dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids.
Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal
testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal
high visible-light photoreactivity, efficient charge transfer and intimate contact interface
for stable cycling and storage purposes. Such a synthetic approach renders
independent thickness and composition control anticipated to advance the development of
‘design-and-build’ 2D layered heterojunctions for large-scale exploration and applications.

1 Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, 117583 Singapore, Singapore. 2 State Key

Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, China. 3 College of Chemistry,
New Campus, Fuzhou University, Fuzhou 350108, China. 4 Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1,
117576 Singapore, Singapore. 5 Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore. Correspondence
and requests for materials should be addressed to G.W.H. (email: [email protected]).

NATURE COMMUNICATIONS | 8:14224 | DOI: 10.1038/ncomms14224 | www.nature.com/naturecommunications 1

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224

U
ltimate two-dimensional (2D) anisotropy with atomically surfactant/intercalator-free exfoliation process, as schematically
thick layered structure is both an ideal low-dimensional illustrated in Fig. 1a (for more details, see Methods). Scanning
system for fundamental study and an elemental building electron microscopy (SEM) images of bulk ZnIn2S4 in Fig. 1b
block for designed assembly1–10. Elaborate functionalities can and Supplementary Fig. 1 reveal a uniform morphology of
rationally be tailored with precise molecular scale control through sheet-like structure. The energy-dispersive X-ray spectroscopy
artificial assembly based on judicious selection and coordination (EDX) (Supplementary Fig. 2) and X-ray diffraction (XRD)
of heterogeneous counterparts11–14. Intriguing surface effects and (Supplementary Fig. 3) analysis confirm the elemental composi-
physical–chemical properties have gradually been uncovered in tion and high purity of the as-synthesized ZnIn2S4 with hexagonal
2D hetero-layered materials owing to their large surface-to- phase structure (cell parameters of a ¼ b ¼ 3.85 Å, c ¼ 24.68 Å,
volume ratio and confined thickness at an atomic scale15–18. JCPDS No. 65–2,023).
The 2D materials, specifically metal chalcogenides, possess Notably, the dispersion of ZnIn2S4 in deionized (DI) water
exquisite photo- and electrochemical capabilities that include reveals a strong negatively charged surface with a zeta potential
energy storage batteries/supercapacitors and energy conversion value of  36.5 mV (Supplementary Fig. 4). This can be ascribed
photo/electrocatalysis systems10,19,20. Unlike electronic transistor to the presence of excess amount of S2  that has been adsorbed
devices, these applications generally require large quantities of 2D onto the ZnIn2S4 surface during the synthesis process34–36. Other
hetero-layered materials. Though a wide variety of 2D layered supporting evidences are appended in Supplementary Figs 5
semiconductor materials have been exfoliated into individual and 6. The self-surface charge within the layered nanostructure
layers, these layered materials typically undergo large extent of significantly weakens the interaction between ZnIn2S4 interlayers.
swelling phase induced by intercalator or solvation species21–23. Owing to Coulombic repulsion, these layers repel each other and
Realization of high-volume exfoliation with ultrathin sheet-like are readily exfoliated with the assistance of shear forces triggered
crystallite in a facile manner and clean medium still remains by mild sonication in the absence of any intercalator and
scarce. Moreover, the issue of lattice mismatching hinders surfactant species (Supplementary Fig. 7).
composition customization of heterostructures owing to the Transmission electron microscopy (TEM) images (Fig. 1c and
ineffective direct epitaxial growth of some mismatched metal Supplementary Fig. 8) of the as-exfoliated ZnIn2S4 layers display
chalcogenide materials. Collectively, all the aforementioned issues 2D sheet structure with a nearly transparent feature, implying the
limit the scalability of 2D ultrathin hetero-layered metal ultrathin nature of the exfoliated product. This self-surface charge
chalcogenides towards fundamental exploration and advanced promoted exfoliation can be corroborated by the controlled
functional applications. experiment of ultrasonic exfoliation of ZnIn2S4 synthesized from
Herein, we readily exfoliate the metal chalcogenide semicon- the addition of a stoichiometric amount of S2  (denoted as
ductor ZnIn2S4 into single-unit-cell layered structure (ca. 2.5 nm) ZnIn2S4-S, see Methods for more details), as illustrated in
via a self-surface charge exfoliation in pure water medium. Supplementary Fig. 9. The as-obtained ZnIn2S4-S displays a weak
Successive electrostatic coupling with another transition metal zeta potential of  5.2 mV (Supplementary Fig. 10). Accordingly,
chalcogenide (for example, MoSe2) enables construction of the dispersion of ZnIn2S4-S can be easily centrifuged after
arbitrary ultrathin hetero-layered hybrids in a large scale. Such ultrasonication. The TEM image in Supplementary Fig. 11
an approach offers salient features, that is, independent thickness demonstrates that the ZnIn2S4-S is composed of aggregated
and composition control of individual layer assembly, and no layers. In addition, negatively charged ZnIn2S4 surface can also be
constraint by lattice matching prerequisite into functional validated by a layer electrostatic self-assembly demonstration of
ultrathin heterostructures. Distinct emission lifetime reduction the ZnIn2S4 nanosheets on positively charged 3-aminopropyl-
and photoluminescence quenching of the hetero-layered hybrid triethoxysilane (APTES)-modified glass substrate (Supplementary
ascertain strong interlayer coupling and efficient charge transfer Figs 12 and 13). Correspondingly, a pale yellow thin film can be
between the components. Surface and interfacial-dominated observed only for the strong negatively charged ZnIn2S4
photocatalysis, a promising strategy for solar energy (  36.5 mV) coating on the glass surface. SEM image reveals
conversion24–32, is adopted to demonstrate the reliability of the uniform coverage/assembly of strong negatively charged ZnIn2S4
catalytically rich 2D ultrathin ZnIn2S4/MoSe2 hetero-layered nanosheets on the positive APTES-glass substrate. Conversely, no
material. The as-synthesized ZnIn2S4/MoSe2 concurrently realize obvious adsorption of the weak negatively charged ZnIn2S4-S
efficient separation and transfer of photogenerated charge carriers, (  5.2 mV) has been observed on the glass substrate. Altogether,
acceleration of surface proton reduction with abundant active sites these findings confirm the existence of strong negatively
as well as enhanced visible light absorption that circumvent the self-charged ZnIn2S4 surface that facilitates facile interlayer
limitations of conventional photocatalysts33. Consequently, the exfoliation of ultrathin ZnIn2S4 nanosheets without the assistance
ZnIn2S4/MoSe2 displays high-performance visible-light-driven H2 of surfactant/intercalator additives.
evolution activity of 6,454 mmol g  1 h  1, B15 and 4 times as high Moreover, the corresponding selected-area electron diffraction
as that of bulk and bare ZnIn2S4 nanosheets, respectively. pattern in Fig. 1c inset shows clear bright spots that correspond to
Importantly, the 2D hetero-layered hybrid shows high stability the hexagonal structure and single-crystalline characteristic of the
with prolonged 80 h cycling and catalytic reactivity retention after ultrathin ZnIn2S4 nanosheets. In addition, the high-resolution
storing over a few months that further attests to the integrity of the TEM (HRTEM) image in Fig. 1c inset displays distinct lattice
constructed 2D materials for prospective advanced applications. fringes of ca. 0.32 nm, corresponding to the (102) crystallographic
Furthermore, we test the applicability of this approach on other plane of ZnIn2S4. The typical Tyndall effect observed for the
2D metal sulfides, namely CdIn2S4 and In2S3 that also show as-exfoliated ZnIn2S4 suspension using a red laser (Fig. 1b, inset)
scalable self-surface charge exfoliation. Similarly, the constructed indicates the formation of freestanding and highly dispersed
hetero-layered hybrids of CdIn2S4/MoSe2 and In2S3/MoSe2 feature ultrathin ZnIn2S4 layers. More importantly, the colloid ultrathin
enhanced photocatalytic activity and stability. ZnIn2S4 nanosheets can be easily exfoliated into large scale
(Supplementary Fig. 14) that is essential for further utilization.
Results TEM characterization cannot unambiguously determine the
Self-surface charge exfoliation of ultrathin ZnIn2S4 layers. The ultimate thickness of the layers. In this context, atomic force
ultrathin single-unit-cell ZnIn2S4 layers were prepared via a facile microscopy (AFM) is used to provide an estimated quantitative
low-temperature refluxing method, followed by a water-assisted layer thickness. As shown in Fig. 1d, the topography of the

2 NATURE COMMUNICATIONS | 8:14224 | DOI: 10.1038/ncomms14224 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224 ARTICLE

Refluxing Exfoliation

Zn S In
Bulk Znln2S4 Single-unit-cell Znln2S4 layers

InCl3 Zn(OOCCH3)2 C2H5NS H2O Ultrasonication

b c d e

Height (nm)
110 102 2 Line 1
2
1 2.54 nm

0
200 300 400 500

Height (nm)
1 2 Line 2
d = 0.32 nm
(102)
1 2.51 nm
0
200 300 400
Distance (nm)

Figure 1 | Schematic illustration of the synthesis of single-unit-cell ZnIn2S4 layers and characterization. (a) A self-surface charge promoted exfoliation
of clean and freestanding single-unit-cell ZnIn2S4 layers in surfactant/intercalator-free medium. (b) Scanning electron microscopy (SEM) image of bulk
ZnIn2S4. Scale bar, 2 mm (c) Transmission electron microscopy (TEM) image of single-unit-cell ZnIn2S4 layers. Scale bar, 50 nm. (d) Atomic force
microscopy (AFM) image and (e) corresponding height images of single-unit-cell ZnIn2S4 layers. Scale bar, 200 nm. The inset in b is photograph of Tyndall
effect of the ZnIn2S4 suspension; insets in c are the corresponding selected-area electron diffraction (SAED) pattern and high-resolution TEM (HRTEM)
image of single-unit-cell ZnIn2S4 layers.

as-prepared ZnIn2S4 presents 2D structure with smooth surface. topography reveals the ultrathin structure of the exfoliated
The corresponding height profiles in Fig. 1e show that the typical CdIn2S4 with the thickness of B2.3 nm (Supplementary Fig. 20).
thickness of the as-exfoliated layers is B2.5 nm, validating the Typical Tyndall effect is observed for the as-exfoliated CdIn2S4
ultrathin nature of the ZnIn2S4. Considering that the c parameter suspension (Supplementary Fig. 21), indicating the formation
of ZnIn2S4 is 24.68 Å (Supplementary Fig. 15), the thickness of of large-scale freestanding and highly dispersed CdIn2S4 layers.
ZnIn2S4 is well in agreement with the thickness of a unit cell Moreover, the respective EDX and XRD analyses in
along the [001] axis37. Thus, it is reasonable to deduce that each Supplementary Figs 22 and 23 confirm the as-synthesized
ultrathin ZnIn2S4 nanosheet with a thickness of ca. 2.5 nm is a CdIn2S4 nanosheets with cubic phase structure (JCPDS No.
single-unit-cell ZnIn2S4 atomic layer. According to the diffusion 27-0060).
formula of t ¼ d2/k2D (d is the particle size, k is a constant, Likewise, this self-surface charge strategy is also exploited to
D is the diffusion coefficient of electron–hole pairs)5,7, the exfoliate In2S3 into a large-scale colloidal dispersion of ultrathin
ultrathin single-unit-cell ZnIn2S4 atomic layer will significantly nanosheets (Supplementary Fig. 24). Zeta potential measurement
shorten the diffusion length and time of charge carriers taken to displays a strong negatively charged surface (zeta potential of
reach the surface, enable the photoexcited electron–hole pairs  41.9 mV) of In2S3 (Supplementary Fig. 25). TEM images in
to transport from the interior to the surface fast, and thus lead to Supplementary Fig. 26 show 2D sheet structure with distinct
higher charge separation efficiency of the ultrathin ZnIn2S4 than lattice fringes (ca. 0.32 nm) of In2S3 (311) crystallographic
its counterpart of bulk ZnIn2S4, as verified by the photocurrent plane. The thickness of the obtained In2S3 is B4.5 nm
and photoluminescence (PL) analysis in Supplementary Figs 16 (Supplementary Fig. 27). Moreover, EDX result confirms the
and 17. elemental composition of In2S3 and XRD pattern reveals the pure
cubic phase of the synthesized In2S3 (JCPDS No. 65-0459)
Generalized synthesis of ultrathin CdIn2S4 and In2S3 layers. (Supplementary Figs 28 and 29).
The suitability of self-surface charge exfoliation as a general
approach for large-scale preparation of other 2D metal sulfides, Construction of hetero-layered hybrids. Recent advances in
that is, CdIn2S4 and In2S3, has also been demonstrated. As shown creating heterostructures based on 2D atomic crystals by artificial
in Supplementary Fig. 18, the CdIn2S4 dispersion in DI water combination of various 2D materials have shown to strongly
shows a strong negative charge with a zeta potential value of modulate electronic and optical properties17. By virtue of the
 39.7 mV. TEM images in Supplementary Fig. 19 demonstrate 2D configuration with large surface area, along with its
the 2D sheet structure of the exfoliated CdIn2S4 nanosheets complementary high interfacial contact with other components,
without using any surfactant or intercalator under moderate the single-unit-cell ZnIn2S4 layers provide a favourable platform
ultrasonication. The inset in Supplementary Fig. 19 shows for the fabrication of hybrid composite17,38. In this context,
HRTEM image where the distinct lattice fringes of 0.33 nm MoSe2 nanosheets are integrated with the ultrathin ZnIn2S4 via a
correspond to the (311) crystallographic plane of CdIn2S4. AFM surface charge promoted self-assembly method that is driven by

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224

strong electrostatic attraction between the negatively charged peaks (Supplementary Fig. 34) could be ascribed to the relatively
ZnIn2S4 layers and positively charged MoSe2 (see Methods for low diffraction intensity of MoSe2 peaks shielded by the strong
more details). The electrostatic self-assembly method efficiently and broad peaks of ZnIn2S4. Notably, Fig. 3d shows the Raman
circumvents the requirement of lattice matching of two individual spectra of ZnIn2S4 and ZnIn2S4/MoSe2 where a characteristic
layers for assembling hetero-layer structure39,40. Consequently, peak at 240 cm  1 corresponding to the ‘A1g’ band of MoSe2
a large quantity of hetero-layered ZnIn2S4/MoSe2 can be facilely (refs 44,48,49) (Supplementary Fig. 35) is observed for ZnIn2S4/
obtained (Supplementary Fig. 30). Moreover, this method MoSe2 sample, confirming the formation of a composite with
also imparts strong hetero-interlayer coupling that effectively MoSe2 in the matrix of ZnIn2S4. In addition, the shift of the ‘A1g’
promotes interfacial charge carriers transfer41–43 that will be band of ZnIn2S4/MoSe2 as compared with that of bare MoSe2
discussed later. (241.1 cm  1) also implies the reduced layer aggregation of MoSe2
Figure 2a,b shows the TEM images of MoSe2, indicating that nanosheets in the hybrid composite48,49. The ultraviolet–visible
the sheets are typically composed of 2–4 layers with an interlayer (UV–vis) absorption spectra in Supplementary Fig. 36 show
spacing of 0.65 nm that corresponds to the (002) plane of that the ZnIn2S4/MoSe2 displays enhancement in visible-light
hexagonal MoSe2 (refs 44,45). The HRTEM image in Fig. 2c absorption as compared with ZnIn2S4. This can be attributed to
shows a d spacing of 0.28 nm that matches with the interspacing the intrinsic background absorption of black-coloured MoSe2
of (100) MoSe2 (refs 46,47). After the integration of MoSe2 (Supplementary Fig. 37). To further determine the composition
with the single-unit-cell ZnIn2S4 layers, the as-prepared and chemical states of the composite, the ZnIn2S4/MoSe2 has
ZnIn2S4/MoSe2 yields a hetero-layered structure (Fig. 2d,e). been characterized by X-ray photoelectron spectroscopy (XPS).
Figure 2f and Supplementary Fig. 31 show HRTEM images of The doublet peaks for Mo 3d at 228.7 and 231.9 eV (top panel of
ZnIn2S4/MoSe2 that display interlayer spacing of MoSe2 Fig. 3e) can be assigned to the Mo þ 4 valence state, whereas the
(0.65 nm) and distinct lattice fringes of ZnIn2S4 (0.32 nm), peak at 226.4 eV should be assigned to S 2s (ref. 15). In the Se 3d
confirming the co-existence and interfacial contact of the XPS spectrum (bottom panel of Fig. 3e), the peaks at 54.4
two components. In addition, Supplementary Fig. 32 shows and 55.3 eV are ascribed to Se2  (ref. 47). Meanwhile, the high-
overlapping TEM mapping of various elements, also indicating resolution XPS spectra of Zn 2p peaks at 1021.8 and 1044.8 eV,
the lamellar structure formation of vertically coordinated ZnIn2S4 In 3d peaks at 445.0 and 452.6 eV and S 2p at 161.9 and 163.0 eV
and MoSe2 heterostructure. The corresponding EDX spectrum (Supplementary Fig. 38) can be assigned to Zn2 þ , In3 þ and S2 
(Fig. 3a) shows the coexistence of Zn, In, S, Mo and Se elements, of ZnIn2S4, respectively50–52. The XPS analysis corroborates the
whereas the EDX mapping (Fig. 3b) demonstrates the presence of MoSe2 in the ZnIn2S4/MoSe2 composite.
homogeneous distribution of these elements throughout the
ZnIn2S4/MoSe2 composite. Therefore, based on the above Photoelectrochemical properties. It has been well accepted that
analyses, it is reasonable to infer that the ultrathin single-unit- layered transition metal chalcogenides with exposed edge sites
cell ZnIn2S4 layers are intimately coupled with the layered MoSe2 can effectively decrease activation energy/overpotential of redox
featuring a sheet-on-sheet hetero-layer structure, as schematically reaction17 that are desirable for photo-/electrocatalytic processes.
reflected in Fig. 3c. According to the energy band structures of ZnIn2S4 and MoSe2,
Moreover, the XRD patterns of ZnIn2S4 and ZnIn2S4/MoSe2 the photogenerated electrons from the excitation of ZnIn2S4
composite (Supplementary Fig. 33) present analogous diffraction are thermodynamically available for transferring to MoSe2.
peaks of hexagonal phase ZnIn2S4. The absence of typical MoSe2 Therefore, it is anticipated that the ZnIn2S4/MoSe2 hetero-

a b c

4 layers

2 layers 2 layers

3 layers
d = 0.28 nm
MoSe2 (100)

d e f

ZnIn2S4 MoSe2
(002) layers
MoSe2 layers

Znln2S4 (102)
2.5 d = 0.32 nm
MoSe2 layers nm

0.65
nm

Figure 2 | Morphology and structure of few-layered MoSe2 and hetero-layered ZnIn2S4/MoSe2. (a,b,d,e) Transmission electron microscopy (TEM)
images of few-layered MoSe2 (a,b) and hetero-layered ZnIn2S4/MoSe2 (d,e). Scale bar, 10 nm. (c,f) High-resolution TEM (HRTEM) images of MoSe2
(c) and ZnIn2S4/MoSe2 (f). Scale bar, 2 nm. The inset in e is the magnification of the image shown in the black box of Fig. 2e. Scale bar, 2 nm.

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224 ARTICLE

a b

Intensity (a.u.)
Mo Mo
S Mo
Cu
Intensity (a.u.)

Zn In

Zn In
Cu 17 18 19 20
Energy (KeV)
Zn
Se Cu
Se
Se Mo Mo

2 4 6 8 10 12 14 16 18 S Mo Se
Energy (KeV)

c d e
S 2s Mo 3d
MoSe2 A2g 226.4
Se-Mo-Se
239.9 cm–1 3d5/2

Counts
228.7 3d3/2
231.9
Znln2S4/MoSe2
Intensity (a.u.)

225 228 231 234

3d5/2 Se 3d
54.4 3d3/2

Counts
55.3
Znln2S4

S-Zn-S-In-S-In-S 200 300 400 500 600 700

54 56 58
Wavenumber (cm–1)
Binding energy (eV)

Figure 3 | Characterization of hetero-layered ZnIn2S4/MoSe2. (a) Energy-dispersive X-ray (EDX) spectrum and (b) mapping images of the as-prepared
ZnIn2S4/MoSe2. Scale bar, 200 nm. (c) Schematic illustration of the sheet-on-sheet ZnIn2S4/MoSe2 hetero-layer structure. (d) Raman spectra of
ZnIn2S4 and ZnIn2S4/MoSe2. (e) High-resolution X-ray photoelectron spectroscopy (XPS) spectra of Mo 3d and Se 3d.

layered structure not only promotes charge separation and t2 is caused by the recombination of free excitons in the ZnIn2S4).
transport driven by junction/interface between the MoSe2 and the For ZnIn2S4/MoSe2, the emission lifetimes of both components
light harvester ZnIn2S4, but also facilitates the proton reduction (t1 ¼ 0.31 ns, t2 ¼ 0.38 ns) are shorter than that of the
on the surface of MoSe2. To gain more insight into its corresponding bulk ZnIn2S4 counterpart (t1 ¼ 0.73 ns,
optoelectronic properties, a series of complementary photo- and t2 ¼ 3.77 ns). The average emission lifetime (calculated from
electrochemical characterizations were carried out. Figure 4a Supplementary Note 1, Supplementary Equation 2), which
displays the linear sweep voltammetry curves of ZnIn2S4/MoSe2 reflects the overall emission decay behaviour of sample, has also
composite and bulk ZnIn2S4, revealing a higher cathodic current displayed an obvious decrease for ZnIn2S4/MoSe2 (2.43 ns) as
density that is attributed to the reduction of water to H2 (ref. 53) compared with that of bulk ZnIn2S4 (3.78 ns). Meanwhile, the
over hetero-layered ZnIn2S4/MoSe2 than bulk ZnIn2S4. steady-state PL spectra in Fig. 4d show obvious PL quenching of
Simultaneously, the controlled experiment over bare fluoride tin hetero-layered ZnIn2S4/MoSe2 hybrid. The corresponding
oxide (FTO) shows no obvious cathodic current under the same observations of PL quenching and lifetime reduction suggest
potential range (Supplementary Fig. 39). The result indicates that the establishment of an electron transfer channel from ZnIn2S4
the integration of MoSe2 with ZnIn2S4 accelerates the protonation to MoSe2 in a nonradiative quenching pathway (Fig. 4c)54,55.
and subsequent H2 formation rate of ZnIn2S4/MoSe2 as compared Accordingly, this leads to efficient interfacial charge transfer
with that of bulk ZnIn2S4. and suppression of photoexcited charge recombination in the
In addition, Fig. 4b displays the time-resolved photo- hetero-layered ZnIn2S4/MoSe2 structure.
luminescence spectra of bulk ZnIn2S4 and hetero-layer structured Furthermore, the electrochemical impedance spectrum of
ZnIn2S4/MoSe2, which probe the specific charge carrier dynamics ZnIn2S4/MoSe2 (Fig. 4e) shows a smaller semicircular in the
of nanosystems54,55. The emission decay curves of the samples Nyquist plot than that of bare ZnIn2S4 nanosheets, indicating a
are fitted by biexponential kinetics function (Supplementary lower charge-transfer resistance in the hybrid composite that
Note 1, Supplementary Equation 1) in which two decay warrants efficient transportation and separation of charge
components are derived (insets in Fig. 4b) (t1 is originated carriers56–59. As shown in Fig. 4f, the ZnIn2S4/MoSe2 displays
from the nonradiative recombination of charge carriers in the obvious transient photocurrent response under visible light
defect states of ZnIn2S4, whereas the longer lifetime component of irradiation. The current density is comparable to recently

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224

a b c
0 1.0 Bulk Znln2S4 Znln2S4/MoSe2

Normalized intensity (counts)

CB e– e– e– KET
1 = 0.73 ns, A1 = 61.65% 1 = 0.31 ns, A1 = 94.91%
1 2
0.8 2 = 3.77 ns, A2 = 38.34% 2 = 0.38 ns, A2 = 5.09%
–2 e–
Ave. = 3.78 ns
j (mA cm–2)

Ave. = 2.43 ns

Energy level
0.6
MoSe2
–4
Bulk Znln2S4 0.4
Znln2S4/MoSe2 Znln2S4
–6 0.2

0.0 VB h+ h+ h+
–0.8 –0.7 –0.6 –0.5 –0.4 –0.3
0 2 4 6 8 10 0 2 4 6 8 10
Potential/ V versus SCE
Time (ns) Time (ns)

d e 120 f
6
Bulk Znln2S4 Bulk Znln2S4 Bulk Znln2S4 Znln2S4/MoSe2
On Off

Photocurrent (μA cm–2)

Znln2S4/MoSe2 100 Znln2S4/MoSe2 5
PL intensitity (a.u.)

80 4
Z′′ (Ω)

60 3

40 2

20 1

0 0
400 450 500 550 600 650 700 0 20 40 60 80 100 120 100 200 300 400 500
Wavelength (nm) Z′ (Ω) Irradiation time (s)

Figure 4 | Photoelectrochemical properties. (a) Linear sweep voltammetry (LSV) curves, (b) time-resolved transient photoluminescence (PL) decay
(excitation at 400 nm and emission at 495 nm), (c) schematic illustration of the interfacial charge carrier transfer, (d) steady-state PL spectra,
(e) electrochemical impedance spectroscopy Nyquist plots and (f) transient photocurrent responses of bulk ZnIn2S4 and hetero-layered ZnIn2S4/MoSe2
composite. CB, conduction band; VB, valence band.

reported 2D-based photocatalyst systems (Supplementary ZnIn2S4 is also demonstrated to be much higher than the
Table 1). In addition, it is notable that the ZnIn2S4/MoSe2 H2 generation rate of the hydrothermal synthesized ZnIn2S4
displays ca. 22-fold photocurrent enhancement as compared with nanoflowers (Supplementary Fig. 40) of ca. 260 mmol g  h  1.
bulk ZnIn2S4 under the same experimental condition, and this is The augmented photoactivity of ZnIn2S4 nanosheets can be
a marked improvement that suggests the structure and attributed to its unique 2D ultrathin structure that lowers
composition advantage of the hetero-layered ZnIn2S4/MoSe2 charge-transfer resistance and shortens the diffusion pathway of
composite in promoting the separation and transportation of charge carriers, thus favouring the fast and efficient separation of
photogenerated charge carriers. Collectively, these commendable photogenerated charge carriers (Supplementary Figs 16 and 17).
photo- and electrochemical properties support efficient Furthermore, significant improvement in H2 generation was
electron–hole pair separation and high surface reaction rate of established after coupling of MoSe2 layers to the ultrathin ZnIn2S4
the ZnIn2S4/MoSe2 hetero-layered structure. nanosheets forming hetero-layered composites. The amount of
H2 evolved increases with MoSe2 content up to 1% (Fig. 5b). The
Photocatalytic H2 production performance. Recent experi- as-obtained ZnIn2S4/1%MoSe2 displays the highest H2 evolution
mental results and theoretical predictions suggest that metal rate of 6,454 mmol g  1 h  1, that is B15 and 4 times as high as
chalcogenides are a class of promising inexpensive, earth- that of bulk ZnIn2S4 and ZnIn2S4 nanosheets, respectively.
abundant and visible responsive catalyst alternatives. However, Notably, the photoactivity is considerable higher than that
nonoptimal interfacial contact and bulk metal chalcogenides of the reference photocatalysts, that is, ZnIn2S4/1%Pt
structure limit catalytic activity owing to poor electronic coupling (4,353 mmol g  1 h  1) and ZnIn2S4/1%MoS2 (3,860 mmol g  1 h  1),
effect and low active sites exposure. Correspondingly, the as shown in Fig. 5c,d. Pt and MoS2 are two exemplary
constructed metal chalcogenide heterostructure that is thinned co-catalysts that have been used in reported literature for
down to a few layers with incorporated electrostatic coupling is photocatalytic H2 evolution. The result highlights the effective-
evaluated by photocatalytic H2 production. The photocatalytic ness of MoSe2 that surpasses the classic Pt and MoS2, as a
performance provides a useful and explicit evaluation to assert the co-catalyst in promoting photocatalytic H2 evolution44,60.
structural integrity and stability of the 2D hetero-layered Importantly, the hetero-layered ZnIn2S4/MoSe2 displays good
structure. stability. The cycling test over the optimal ZnIn2S4/1%MoSe2
The photocatalytic activity, H2 generation of the ultrathin (Fig. 5e) shows negligible photoactivity loss after 20 consecutive
ZnIn2S4 layers and ZnIn2S4/MoSe2 hetero-layered nanohybrids cycles with accumulatively 80 h under visible light irradiation.
was performed under visible light irradiation (l4400 nm) Moreover, after storing in ambient conditions for 3 months, the
using lactic acid as the hole scavenger. As shown in Fig. 5a, the ZnIn2S4/1%MoSe2 retains a high photoactivity as that of the fresh
single-unit-cell ZnIn2S4 layers show a H2 evolution rate of sample (Supplementary Fig. 41). The high photoreactivity and
B1,748 mmol g  1 h  1 that is fourfold of the pristine bulk stability of the 2D hetero-layer ZnIn2S4/1%MoSe2 hybrid provide
ZnIn2S4 (446 mmol g  1 h  1), indicating enhanced activity of direct evidence of the large exposed active surface and strong
the ultrathin layers. In addition, the photoactivity of the ultrathin electronic coupling between the interlayers.

6 NATURE COMMUNICATIONS | 8:14224 | DOI: 10.1038/ncomms14224 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224 ARTICLE

a b c
7,000 7,000
1,800
6,000 6,000
H2 evolution rate (μmol g–1 h–1)

H2 evolution rate (μmol g–1 h–1)

H2 evolution rate (μmol g–1 h–1)

1,500
5,000 5,000
1,200
4,000 4,000

900
3,000 3,000

600 2,000 2,000

300 1,000 1,000

0 0 0
e e e
er n 2S 4 eets ts oS 2 oS 2 MoS 2 oSe 2 Pt
low hee .5%M /1%M Mo
S2 Se 2
nof Znl osh o s / 2 %
/3%
M /1% Mo
na Bu
lk nan nan S
/0
n S4 n S4 S4 ln 2S
4 /1% /1%
l l
ln 2S
4
ln 2S Zn
2 2 n
ln 2S
4 n n l 4
ln 2S Znl
n ln 2S
4 2 4
Zn Zn
4 2 Z Z Zn Zn
Zn Zn

d e
25,000
25,000 Znln2S4/1% MoS2
Znln2S4/1% MoSe2
20,000 Znln2S4/1% Pt 20,000
H2 amount (μmol g–1)

H2 amount (μmol g–1)

15,000 15,000

10,000 10,000

5,000 5,000

0 0
0 1 2 3 4 0 10 68 76
Irradiation time (h) Irradiation time (h)

Figure 5 | Photocatalytic H2 production performance. (a,b) Photocatalytic H2 evolution over ZnIn2S4 nanoflowers, bulk ZnIn2S4 and single-unit-cell
ZnIn2S4 layers (a), and ZnIn2S4/MoSe2 composites with different weight ratios of MoSe2 (b). (c,d) Comparison of photocatalytic H2 evolution activities
over ZnIn2S4/1%Pt, ZnIn2S4/1%MoS2 and ZnIn2S4/1%MoSe2. (e) Recycling photoactivity test of ZnIn2S4/1%MoSe2. Note that the error bars represent the
photoactivity s.d. values calculated from triplicate experiments.

Besides, photocatalytic H2 activities of ultrathin CdIn2S4 and ultrathin and intimate interface characteristics, guided by
In2S3 layers also exceed that of their bulk counterparts unconstraint electrostatic coordination of a dissimilar metal
(Supplementary Fig. 42). Self-assembly construction of 2D chalcogenide, is demonstrated in this work. In contrast, thin-film
hetero-layer hybrids, that is, CdIn2S4/MoSe2 and In2S3/MoSe2, epitaxial growth is strongly influenced by the surface of the
also verifies the enhanced photoactivity and stability. Essentially, substrate and degree of lattice matching. This limits the
the coupling of ultrathin CdIn2S4 and In2S3 with a few layers of production yield and imposes a high cost of 2D hetero-layer
MoSe2 co-catalyst has enhanced the H2 evolution activity metal chalcogenide for practical implementation. To test the
(Supplementary Fig. 43). The rates of H2 evolved over the hypothesis of the satisfactorily high quality of the as-prepared 2D
optimal CdIn2S4/1%MoSe2 and In2S3/1%MoSe2 are B9- and hetero-layer, surface and interfacial-dominated photocatalysis is
10-fold of bare CdIn2S4 and In2S3 nanosheets, respectively. In used as an ideal testbed for reliability verification. Diverse 2D
addition, the photoactivities of the resulted metal sulfide/MoSe2 ultrathin metal sulfide/MoSe2 hetero-layered materials reveal
(CdIn2S4/1%MoSe2 and In2S3/1%MoSe2) are also much higher outstanding visible-light photoreactivity and efficient charge
than those of the reference photocatalysts, that is, metal sulfide/Pt transfer exceeding that of metal sulfide/Pt and metal sulfide/
and metal sulfide/MoS2 (Supplementary Fig. 44). Furthermore, MoS2 reference photocatalysts. More remarkably, the ultrathin
the cycling tests of the optimal CdIn2S4/1%MoSe2 and hetero-layer structures demonstrate highly stable contact
In2S3/1%MoSe2 show negligible photoactivity degradation after interface promising for long-term cycling and storage purposes.
20 consecutive cycles with accumulatively 80 h under visible light In summary, we have developed a scalable method to
irradiation (Supplementary Fig. 45). artificially coordinate ultrathin metal chalcogenide hetero-layer
structure via a combination of pristine self-surface charge
Discussion exfoliation and electrostatic coupling of dissimilar layers. This
Although prior literature has already reported exfoliated 2D generic approach to the preparation of 2D hetero-layered hybrids
layered metal chalcogenides commonly induced by intercalator is attractive as it allows selection of individual constituent
osmotic swelling, self-surface charge exfoliation into single-unit- materials and thickness control, opening up the possibility of
cell thick layer structure in pure water is unprecedented. ‘design-and-build’ 2D layered heterojunction for large-scale
Successive artificially coupled hetero-layered structure with theoretical exploration and practical applications.

NATURE COMMUNICATIONS | 8:14224 | DOI: 10.1038/ncomms14224 | www.nature.com/naturecommunications 7

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms14224

Methods samples was collected and detected by a photon-counting photomultiplier (PMA,

Materials. Zinc acetate dehydrate (Zn(CH3COO)2  2H2O, Z98%), sodium Picoquant). The emission centred at 495 nm was selected by a monochrometer
molybdate dehydrate (Na2MoO4  2H2O, Z99%) and hydrazine hydrate (SpectroPro 2300i, Princeton Instrument). The PL decay dynamics were achieved
(N2H4  H2O, 99.99%) solution were obtained from Sigma-Aldrich. Indium by a time-correlated single photon counting module (TCSPC Picoharp 300,
chloride (InCl3, 99.995%), L( þ ) lactic acid (90%) and selenium (99.5 þ %) were Picoquant).
obtained from ACROS Organics. Thioacetamide (C2H5NS, 498%) was obtained Photoelectrochemical measurements were performed in a conventional
from TCI. All of the reagents were used as received without further purification. three-electrode quartz cell. A Pt plate was used as counter electrode, and Ag/AgCl
The DI water used in the catalyst preparation was from local sources. electrode/saturated calomel electrode were used as reference electrode, whereas the
working electrode was prepared on FTO conductor glass. The sample powder
(3 mg) was ultrasonicated in 0.5 ml of N,N-dimethylformamide (supplied by
Synthesis of single-unit-cell ZnIn2S4 layers. Single-unit-cell ZnIn2S4 layers were Sigma-Aldrich) to disperse it evenly to get a slurry. The slurry was spread onto
fabricated by a facile low-temperature refluxing method followed by a moderate FTO glass with the area of 1 cm2. After air drying, the working electrode was
exfoliation. In detail, 1.5 mmol of Zn(CH3COO)2  2H2O and 3 mmol of InCl3 were further dried at 90 °C for 2 h to improve adhesion. The electrolyte was 0.2 M
added into 250 ml DI water and stirred for 30 min. Subsequently, an excess amount aqueous Na2SO4 solution (pH ¼ 6.8). Linear sweep voltammetry curves were
of thioacetamide (TAA, 8 mmol) was added into the above solution and stirred for performed in a mixed solution of 10% (v/v) lactic acid and 0.2 M aqueous Na2SO4
another 30 min. The solution was then heated to 95 °C and maintained at that solution.
temperature for 5 h under vigorous stirring. The resulted precipitation was
collected by centrifugation, rinsed with water for 2 times and re-dispersed into
200 ml DI water. The dispersion was sonicated continuously for 30 min and then Photocatalytic H2 evolution measurements. With the aid of ultrasonication,
centrifuged at 6,000 r.p.m. for 5 min to remove aggregates. After that, the colloidal 5 mg of photocatalyst, 9 ml DI water and 1 ml lactic acid were mixed in a 25 ml
single-unit-cell ZnIn2S4 layers were obtained. For each set of experimental quartz cylindrical reaction cell to form a homogeneous suspension. Then, the
synthesis, B0.6 g of ZnIn2S4 can be obtained. The comparative sample of reactor was purged with argon gas for 10 min before illumination with a 300 W
ZnIn2S4-S was synthesized via the same procedure except that a stoichiometric xenon arc lamp (l4400 nm). The evolved H2 was analysed using an online gas
amount of TAA (6 mmol) was added during the synthesis process. chromatograph (GC-2014AT, Shimadzu Co., Japan) equipped with a thermal
conductivity detector.
The recycling test of catalytic H2 evolution over the as-prepared photocatalyst
Synthesis of hetero-layered ZnIn2S4/MoSe2 structure. MoSe2 was synthesized was performed as follows. After the reaction of the first run under visible light
via a one-step hydrothermal method44. The surface modification of MoSe2 was irradiation, the suspension was purged with argon gas for 10 min. The process
carried out as follows: 50 mg MoSe2 was dispersed in 100 ml ethanol and sonicated was carried out for four more cycles. After every five cycles, the photocatalyst
continuously for 1 h. Then, 0.25 ml of APTES was added into the above MoSe2 was centrifuged and mixed with fresh 9 ml DI water and 1 ml lactic acid for
dispersion. The mixture was heated at 60 °C for 4 h under mild stirring. The continuous test.
resulted product was rinsed with ethanol for 3 times and redispersed in 100 ml DI
water with the aid of ultrasonication for 1 h. After that, the dispersion was
centrifuged at 6,000 r.p.m. for 5 min to remove aggregates. Then, the colloid Data availability. The data that support the findings of this study are available
APTES-modified MoSe2 with positive surface charge was obtained. The 2D hetero- from the corresponding author on request.
layer composite can be built up by dipping of MoSe2 nanosheet suspension into
colloidal ZnIn2S4 of constraint supply or controlled amount of dilute solution. In
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