Accepted Article

Title: Scalable MoS2/Black Phosphorus Heterostructure for pH-

Universal Hydrogen Evolution Catalysis

Authors: Tingting Liang, Yaoda Liu, Yize Cheng, Fei Ma, and Zhengfei
DAI

This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: ChemCatChem 10.1002/cctc.202000139

Link to VoR: http://dx.doi.org/10.1002/cctc.202000139

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ChemCatChem
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Scalable MoS2/Black Phosphorus
Universal Hydrogen Evolution Catalysis
Tingting Liang[a], Yaoda Liu[a], Yize Cheng[a], Fei Ma*[a] and Zhengfei Dai*[a, b]
[a] T. Liang, Y. Liu, Y. Cheng, Prof. F. Ma, and Prof. Z. Dai
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, China
E-mail: sensdai@mail.xjtu.edu.cn; mafei@mail.xjtu.edu.cn
[b] Prof. Z. Dai
State Key Laboratory for Powder Metallurgy, Central South University, Changsha 410083, China
Supporting information for this article is given via a link at the end of the document.
Abstract. The exploration and scalable synthesis of the earth-
abundant and excellent electrocatalysts without noble metal are
crucial to the future hydrogen production and application. Herein, an
affordable electrocatalyst is built through an in-situ growth of MoS2
nanosheets vertically on the electro-exfoliated black phosphorus
(EEBP) for hydrogen evolution reaction (HER). The electro-exfoliation
achieves the high-yield production of few-layer BP lamellae from its
bulk crystal, hosting the scalable synthesis of uniform MoS2/EEBP
heterostructure. Moreover, the vertical growth manner can effectively
aggrandize the exposed MoS2 edge sites and probably advance the
catalytic activity to a certain extent. As for HER, such a MoS2/EEBP
heterostructure exhibits promising catalytic performance with low
overpotentials of 126 mV, 237 mV and 258 mV at 10 mA cm-2 (η10) as
well as low Tafel slopes in both acid, alkaline and neutral media,
respectively. The rationales behind the satisfactory catalytic
properties are explained by density functional theory (DFT)
calculations. Theoretically, it is revealed that the MoS2/EEBP
heterostructure with a more neutral hydrogen adsorption energy can
benefit the electrons migration and boost the water dissociation
kinetics. This study presents an effective method to design and
fabricate highly efficient heterostructure electrocatalysts through
interface engineering towards hydrogen production.
Introduction
The sustainable and renewable hydrogen (H2) has drawn
extensive attention in recent years as it is a promising candidate
for replacing traditional fossil fuels.[1] Water electrolysis is
currently the most employable approach for hydrogen production
with high purity, in which Pt-based materials were acknowledged
as the benchmark catalysts for boosting the H2 evolution reaction
(HER).[2] But their rareness and exorbitant price would impede the
scalable implementation of H2 energy seriously.[3] Therefore,
design and exploration of non-precious catalysts with high
electrocatalytic activity is of significance to the future H2
economy.[4] In view of this, a diverse range of catalysts based on
transition metals have been investigated and admitted as
functional HER electrocatalysts, including but not limited to their
phosphides, carbides, nitrides and sulphides.[5] Among them,
transition metal dichalcogenides (TMDs, e.g. MoS2) are regarded
as potential electrocatalysts in HER with considerable catalytic
performance, due to their tunable band gap and controllable
layered structure.[6] Previous reports accord that HER activity of
TMD is generally raised from its highly energetic edge sites.
However, such edge sites in the entire TMD structure just occupy
1
This article is protected by copyright. All rights reserved.
10.1002/cctc.202000139
Heterostructure for pH-
Accepted Manuscript
a small proportion, leading to a hinderance to the full play of its
instinct catalytic property.[7] On account of this, a consensus in the
community is to make an vast exposure of the active TMD edge
sites to promote the HER process.[8]
In the past years, several methods have been testified to
effectively boost the catalytic action of TMDs,[9] such as
morphological control,[10] defect engineering,[11] and interface
engineering.[12] These methods can grant the improvement of
HER performance to a certain extent through aggrandizing the
exposed S active sites.[13] In particular, interface engineering has
been regarded as one of the most performable strategies to
enhance the actual TMDs catalytic properties, with a view to both
the edge exposure and charge transfer at the interface.[14] It is
suggested that the charge transfer rate can be accelerated
effectively through interface formation and further regulate the
electron distribution.[15] For instance, a MoS2/graphene nanosheet
heterostructure demonstrated by Meng et al. has exhibited much
better acidic HER property with an η10 overpotential of 185 mV
than that of bare MoS2.[16] But the recognized hydrophobic nature
of graphene would hamper water adsorption capacity and make
a depression to the electrocatalytic activity.[17] Searching new type
of hydrophilic and active host substrate is deemed as an
appropriate choice to cope with the sluggish water dissociation
kinetics.[18] One material that holds the promise is two-
dimensional black phosphorus (BP), which has been attracted
growing interest in HER for its hydrophilic behavior and
electrochemical activity.[19] He et al. has substantiated the
effectiveness of liquid-exfoliated BP (LEBP) nanosheet as the
host material to direct MoS2 nanoparticles with much enhanced
HER activity.[20] Analogously by van der Waals (vdW) interaction,
Wan et al. fabricated a MoSe2/LEBP heterostructure with
enhanced electrocatalytic properties for HER (η10, 380 mV).[21]
Instead of the weak vdW interaction, a further improvement was
illustrated by Vishnoi et al. by using a covalently linked
phosphorene-MoS2/MoSe2 heterostructure for HER (η10, 330
mV).[22] This clearly features that the increase of interactive
strength between BP and TMDs could effectively promote the
HER electrocatalytic properties. It should be stated that the few-
layer BP yield by liquid exfoliation is too low to stride forward the
practical applications of such BP/TMD electrocatalysts. Hence,
the pursuit of large-scale synthesis method for BP/TMD
heterostructures would be a matter of great significance to
facilitating their deployment in water electrolysis.
In this study, electrochemical exfoliation method was used to
obtain BP nanosheets (EEBP) with high yield (~85%). And then
MoS2/EEBP heterostructure was achieved using a solvothermal
method through in situ growth of MoS2 on the EEBP. In the
ChemCatChem 10.1002/cctc.202000139

FULL PAPER
MoS2/EEBP heterostructure, MoS2 nanosheets with thickness of
3-8 nm distribute evenly along a vertical direction opposite to
EEBP. The vertical MoS2 can help to expose more S edge to
benefit the enhancement of HER performance. The MoS2/EEBP
heterostructure emerges meaningful catalytic capacity for pH-
universal HER reaction in all the alkaline, neutral and acidic
conditions. Particularly, in 0.5 M H2SO4, the on-set potential and
the overpotential at η10 is as low as 67 mV and 126 mV,
respectively. In 0.5 M H2SO4, the Tafel slope of MoS2/EEBP
heterostructure is as low as 68 mV dec-1. The MoS2/EEBP
heterostructure presents favorable stability during long-time
chronopotentiometry (i-t) test. Besides, density functional theory
(DFT) calculations illustrate that the interface between MoS2 and
image in Figure 1e displays the crystal distance of 0.216 nm
corresponding to (002) plane of BP. Figure 1f presents the TEM
morphology of bare MoS2 with a size smaller than 30 nm and the
selected area electron diffraction (SAED) pattern (the inset of
Figure 1f). Bare MoS2 shows flower-like shape self-assembled
from several small nanosheets. TEM image in Figure 1g presents
the morphology of MoS2/EEBP heterostructure. It is clearly
demonstrated that MoS2 nanosheets are uniformly grown on
EEBP. The HRTEM image (Figure 1h) displays a crystal distance
of 0.336 nm in response to (021) plane of BP. And the lattice
fringes within green dotted line manifest the typical folds of MoS2.
The thickness of MoS2 on EEBP is in the range of 3-8 nm (Figure
S2). Moreover, in the SAED of MoS2/EEBP, the (021), (060),

BP can improve the charge exchange rate and reduce the
∗
hydrogen adsorption free energies ( ∆𝐆𝑯 ). The typical 2D-2D
heterostructure reveals promising catalytic activity, and paves the
way for the rational design of scalable and advanced
electrocatalysts through interface engineering.
Results and Discussion
The synthesis process of MoS2/EEBP is illustrated in Scheme 1.
Firstly, the bulk BP crystal was expanded into sponge-like BP
block through a facile electrochemical exfoliation method using
direct-current circuit.[23] And then EEBP nanosheets with few
layers were achieved by sonication with a cell breaker in 5 min
and collected with a high yield of 85%. Further by a solvothermal
method, MoS2 nanosheets could be grown on the both sides of
EEBP vertically, leading to the formation of a MoS2/EEBP
heterostructure.
Accepted Manuscript
(221) and (004) crystal planes of BP, and (006), (0010) crystal
planes of MoS2 can be recognized clearly. The EDX mapping
images are shown in Figures 1j-n, illustrating uniform distribution
of the elements (P, S, and Mo) in the heterostructure. All the
results mentioned above prove the formation of MoS2/EEBP
heterostructure. Besides, the growth process of vertical MoS2
nanosheets on BP is presented in Figure S3. After nucleation and
diffusion of MoS2 on BP, MoS2 islands are formed. And then two
MoS2 islands impinge on each other, forming arch structure to
release the pressure and shaping up vertical MoS2 nanosheets
on BP ultimately.[25]

Scheme 1. Scheme of the formation of MoS2/EEBP heterostructure.

The morphologies of EEBP, MoS2 and MoS2/EEBP are

displayed in Figures 1a-c. The scanning electron microscope
(SEM) image in Figure 1a clearly exhibits the layered structure of
bulk BP crystal. It was further downscaled into few-layer BP
nanosheets by electrochemical exfoliation. The atomic force
microscope (AFM) observation indicates the thickness and lateral
dimension of EEBP are ca. 4.5 nm and beyond 1 µm (Figure S1a-
Figure 1. a-c) SEM images of bulk BP, MoS2, and MoS2/EEBP, respectively; d-
b), respectively. Figure 1b shows the flower-like bare MoS2 e) TEM and HRTEM of EEBP, respectively; f) TEM and SAED (inset) of MoS2;
nanosheets, which are further grown uniformly on the surface of g-i) TEM, HRTEM and SAED of MoS2/EEBP, respectively; j-n) EDX mapping of
MoS2/EEBP.
EEBP nanosheet forming the MoS2/EEBP heterostructure (Figure
1c). The contents of elements of bare MoS2 and MoS2/EEBP are
The structural and valence state information of the samples
detected by energy dispersive X-ray spectrometer (EDX). The
were investigated through X-ray diffraction (XRD) and Raman
S/Mo atom ratio is about 1.68 of MoS2/EEBP, which is much lower
spectra. The XRD patterns of bulk BP and EEBP are show in
than that (2.8) of bare MoS2 (Figure S1c-d). This means the S
Figure 2a, where distinct peaks at 16.9°, 34.2° and
deficiency in MoS2/EEBP heterostructure, which would also
52.3°correspond to (020), (040) and (060) crystal planes of BP
provide more activity sites in the MoS2/EEBP.[24]
(JCPDS no.01-073-1358), respectively. With respect to
In addition, transmission electron microscope (TEM) image
MoS2/EEBP, the peak at 26.5° corresponds to (021) crystal plane
shown in Figure 1d also demonstrates that the EEBP nanosheets
BP. And peaks at 33.4° and 55.6°are respectively in accordance
are uniform and thin. And the high-resolution TEM (HRTEM)

2
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ChemCatChem
FULL PAPER
with (101) and (106) crystal planes of MoS2 (JCPDS. No.00-006-
0097), indicating the formation of MoS2 on the EEBP (Figure 2b).
Raman spectra of EEBP, MoS2 and MoS2/EEBP are further
analyzed in Figure 2c. It presents the common Raman
characteristic lines of Ag breathing mode (Ag1, out-of-plane
direction; Ag2, in-plane armchair direction) and B2g shearing mode
(in-plane zigzag direction) of BP.[26] And also the A1g (breathing
mode) and E2g1 (shearing mode) peaks of MoS2 sample are
Raman characteristic lines of 2H-MoS2. For MoS2/EEBP
heterostructure, two presented characteristic dominant E2g1 and
A1g vibrations at 365.82 cm-1 and 392.4 cm-1 demonstrate the
formation of MoS2 on EEBP. As compared to the EEBP, Ag2 and
B2g vibration modes of MoS2/EEBP hybrid show the Raman peaks
shifted to lower wavenumbers on account of vibrations inhibition,
suggesting an intimately interfacial interaction between EEBP and
MoS2.[21, 22, 27] Besides, increased A1g mode intensity
demonstrates more edge-terminated S sites, since the A1g mode
stands for the out of plane vibration of S atoms which are in
opposite directions (along the c-axis).[28] The peak intensity ratio
of E2g1 to A1g can indicate the edge-exposed degree of MoS2. The
smaller ratio (0.35) of E2g1 to A1g for MoS2/EEBP can imply higher
S edge exposure than bare MoS2 (0.46).[29]
Figure 2. XRD, Raman spesctra and XPS spectrum of BP, MoS2 and
MoS2/EEBP, respectively: a) XRD of bulk BP and EEBP; b) XRD of MoS2 and
MoS2/EEBP; c) Raman spectrum of EEBP, MoS2 and MoS2/EEBP; d) P 2p
spectra of EEBP; e-f) Mo 3d, S 2p spectra of MoS2; and g-i) P 2p, Mo 3d, and
S 2p spectra of MoS2/EEBP.
Moreover, X-ray photoelectron spectroscopy (XPS) was
employed to examine the compositions and surface valence
states of materials. The typical XPS survey spectra for EEBP,
MoS2 and MoS2/EEBP are displayed in Figure S4. Gaussian
curve fitting is employed to deconvolute the spectra. As for bare
EEBP, the couple peaks at 129.8 eV (P 2p3/2) and 130.6 eV (P
2p1/2) can be observed in Figure 2d. Another additional couple
peaks at 133.9 eV and 134.7 eV relate to surface phosphorus
oxidation during the electrochemical exfoliation process. Figure
2e shows the Mo 3d spectrum of bare MoS2. The peaks at 232.0
eV, 228.8 eV and 226.3 eV correspond to Mo 3d3/2, Mo 3d5/2 and
S 2s3/2, respectively. Another couple peaks at 232.9 eV 229.8 eV
could be ascribed to Mo5+, while the weak peak at 235.4 eV is
assigned to Mo6+.[30] With respect to the S 2p spectrum of MoS2
3
This article is protected by copyright. All rights reserved.
10.1002/cctc.202000139
(Figure 2f), The couple peaks at 162.9 eV and 161.9 eV
correspond to terminal S22-, while another couple peaks at 164.3
eV and 163.5 eV present the existence of apical S2- and bridging
S22-.[31] As for MoS2/EEBP, the fitted peaks of P 2p, Mo 3d, S 2s
and S 2p spectra present as Figures 2g-i. Compared with bare
EEBP, the peaks of P 2p3/2 and P 2p3/2 shift up 0.5 eV, illustrating
BP is the electron donor of MoS2/EEBP heterostructure. In
addition, the ratios of phosphate to P-P are 1.95 for MoS2/EEBP
and 2.58 for EEBP, respectively. The less oxidation of
phosphorus in MoS2/EEBP is benefited from the interface
between MoS2 and BP.[32] Meanwhile, it is also calculated that the
content ratios of Mo4+: Mo5+: Mo6+ are 0.56: 0.38: 0.06 and 0.40:
0.54: 0.06 for bare MoS2 and MoS2/EEBP (Figure S5),
Accepted Manuscript
respectively. Higher content of Mo5+ would result in higher
conductivity and enhanced catalytic ability.[33] Besides, the high
terminal S22- content (83.1%) in the MoS2/EEBP represent
abundant edge-terminated S sites and may carry forward the
catalytic performance.[34]
Figure 3. HER performance in 0.5 M H2SO4, 1 M KOH and 1 M PBS,
respectively (in order from left to right): a-c) polarization curves, d-f) tafel plots
of EEBP, MoS2 and MoS2/EEBP and g-h) i-t test of MoS2/EEBP for 24 h.
The HER performances of EEBP, MoS2 and MoS2/EEBP
were shown in Figure 3. As for the linear sweep voltammetry
(LSV) curves in Figures 3a-c, MoS2/EEBP presents lowest onset
overpotential (67 mV, 125 mV, and 133 mV) and overpotentials at
η10 (126 mV, 233 mV and 258 mV) in acid, alkali and neutral
solutions, respectively. At the meantime, the MoS2/EEBP
heterostructure shows the lowest Tafel slopes of 68 mV dec-1
(acid), 99 mV dec-1 (alkali) and 154 mV dec-1 (neutral),
respectively. Moreover, the enhanced HER performance of
MoS2/EEBP can be alternatively explained by electrochemical
impedance spectroscopy (EIS) test shown in Figure S6.
MoS2/EEBP displays the lowest resistance of charge transfer
(Rct) as compared to bare MoS2 and EEBP, meaning fastest
charge exchange rate during the HER reaction. Furthermore, the
mass activity at overpotential of 200 mV is calculated and
displayed in Figure S7. The mass activity of MoS2/EEBP is much
higher than those of bare BP and MoS2, especially in acid
electrolyte. In addition, the stability of MoS2/EEBP in different
solutions during the HER process were detected through i-t tests
for 24 h, as rendered in Figure 3g-I. There is just small
degradation of the current density of MoS2/EEBP after HER for 24
ChemCatChem
FULL PAPER
h. Cyclic voltammetry (CV) curves (Figure S8) also verify the
stable performance during the HER process. Figure S9 shows the
long-time i-t examination of bare MoS2, demonstrating good
stability during 24 h HER process. The structure of MoS2/EEBP
heterostructure was characterized after i-t test, as shown in Figure
S10. It remains nanosheet morphology without obvious
destruction, and also the elements (P, Mo, and S) distribute
uniformly. The structural stability of the MoS2/EEBP during
catalytic reaction is benefit from the uniform distribution of MoS2
around EEBP.
The effective electrochemical active surface area (ECSA) of
catalysts was estimated. From the CV curves (-0.054–0.044 V vs.
RHE) at various scan rates, the double-layer capacitance (Cdl) of
three kinds of catalysts were detected (Figure 4a-c). And the Cdl
was calculated by plotting the current density difference of j
between positive scan and negative scan (Δj) at -0.005 V vs. RHE
against the scan rates. The slopes of fitted lines are double Cdl.
The Cdl values of MoS2/EEBP, MoS2, and EEBP were 46.97 mF
cm-2, 8.86 mF cm-2, and 1.48 mF cm-2, respectively (Figure 4d).
Much larger Cdl value of MoS2/EEBP means higher ECSA,
leading to the improvement of HER performance. Moreover, the
optical contact angle was detected as shown in Figure S11.
MoS2/EEBP sample shows higher hydrophilicity than bare MoS2
and EEBP, which favors the water adsorption and HER reaction.
Figure 4. ECSA for HER process in 0.5 M H2SO4: a) EEBP. b) MoS2, c)
MoS2/EEBP; and d) charging current density differences at different scan rates.
The mechanism of the enhanced HER performance of
MoS2/EEBP heterostructure was investigated in detail through
DFT calculations using VASP software. The model framework is
established starting with a 5×4×1 supercell of BP (020) and a
4×4×1 supercell of MoS2 (001) (Figures 5a-b). The lattice
mismatch between BP (020) and MoS2 (001) surface slab is just
around 1.46 %, verfying slight lattice strains at the MoS2/BP
interface. Firstly, the formation energies of the heterostructures
based on MoS2 and BP were calculated as Equation (1).
𝑬 = 𝑬∗(𝑴𝒐𝑺𝟐 𝑩𝑷) − 𝑬∗𝑴𝒐𝑺𝟐 − 𝑬∗𝑩𝑷
where 𝑬∗(𝑴𝒐𝑺𝟐 𝑩𝑷) is the total energy of the relaxed MoS2/BP
heterostructure, 𝑬∗𝑴𝒐𝑺𝟐 is the total energy of relaxed MoS2 slab,
and the 𝑬∗𝑩𝑷 is the total energy of the relaxed BP slab. The
formation energy MoS2/BP with and without S vacancy is -1.86 eV
and 1.47 eV, attesting that it prefers to form the MoS2/BP
heterostructure with S vacancy. It is stable structure, which is also
in accordance with the experimental results. Thus, the following
This article is protected by copyright. All rights reserved.
10.1002/cctc.202000139
calculations are carried out using bare BP slab, MoS2 slab and
the MoS2/BP heterostructure with S vacancy.
The density of states (DOS) of bare BP, MoS2 and MoS2/BP
were calculated and presented in Figures 5c. The bare BP and
MoS2 show charactistic semiconductive electrical structure, while
MoS2/BP shows metallic properties. The DOS near the Fermi
level of MoS2/BP can promote the charge exchange rate through
HER reactions, resulting in much enhanced catalytic property.
∗
Furthermore, since the hydrogen adsorption free energies (∆𝐆𝑯 )
is deemed as a typical indicator of the HER activity, we have
∗
calculated ∆𝐆𝑯 on the surface of bare BP, MoS2 and the MoS2/BP
heterostructure. With respect to HER process, a single hydrogen
atom is calculated to be absorbed on the P atom of BP, S edge of
Accepted Manuscript
MoS2, and center of the S vacancy of MoS2/BP (Figure S12-S14),
respectively.[35] The ∆𝐆𝑯 ∗
is calculated according Equation S1-S5.
∗
The calculated trend points out the ∆𝐆𝑯 at the MoS2/BP
hetetrostructure (-0.15 eV) is apparently lower than that of bare
BP (1.28 eV) and MoS2 (2.01 eV) as shown in Figure 5d. The
detail informations of calculation process are listed in Table S1,
and it is consistent with the actual trend of HER performance.
Additionally, the work function of MoS2 and BP was calculated
and presented as Figure S15. The work functions of MoS2 with
vacancy and BP are 5.79 eV, and 4.66 eV, respectively. Thus, the
electrons can transfer from p-type BP to n-type MoS2 easily
through the interface, [36] boosting the charge exchange during the
HER process. The corresponding Mott-Schottky plots for
determining the semiconductor types are shown in Figure S16.
Therefore, the MoS2/EEBP heterostructure with large amount of
activity sites and effective interface provides substantial HER
catalytic performance than other reported catalysts based on BP
nanosheets (Table S2).
Figure 5. Schematic diagram of model of MoS2/BP: a) top view and b) cross
view, c) DOS of bare BP, MoS2 and MoS2/BP, and d) hydrogen adsorption free
energies of bare BP, MoS2 and MoS2/BP, respectively.
(𝟏)
Conclusions
To be summarized, a scalable MoS2/EEBP heterostructure with
high catalytic activity is built via an in-situ formation of MoS2 on
electrochemical exfoliated BP with high yield. It is demonstrated
MoS2 nanosheets were found to be grown uniformly and vertically
on the surface of EEBP nanosheet, making a vast exposure of the
active edge sites. The MoS2/EEBP heterostructure has exhibited
4
ChemCatChem
FULL PAPER
considerable catalytic performance with low η10 overpotentials of
126 mV, 237 mV, 258 mV for HER in acidic, alkaline and neutral
electrolytes, respectively. And Tafel slopes are as low as 68, 99
and 154 mV dec-1 in the corresponding media. Such a
MoS2/EEBP heterostructure also brings out substantial long-time
stability in three types of electrolyte as well as higher
electrochemically active surface area. The DFT calculations were
applied to explain the mechanism of the improved catalytic ability
based on MoS2/EEBP heterostructure. It is revealed that the
MoS2-EEBP interface can promote the electrons migration and
boost the water dissociation kinetics. This study presents
fundamental insights into the practically electrocatalytic
implementation of BP nanosheets based 2D-2D heterostructure
through interface engineering.
Experimental Section
Chemicals and methods: bulk BP crystal (99%),
tetrabutylammonium tetrafluoroborate (TBAB, 98%), Ammonia
tetrathiomolybdate ((NH4)2MoS4, 98%), 20 wt.% Pt/C, acetylene
carbon black, dimethyl sulfoxide (DMSO, 99.9%), potassium
hydroxide (KOH, 95%), N, N-dimethylformamide (DMF, 99.5%),
sulfuric acid (H2SO4, 38%), phosphate buffer saline (PBS), Nafion
(5 wt.%) and ethanol (99.9%) were purchased from Sinopharm.
Deionized water was obtained from a Millipore Autopure system
(18.2 MΩ‧cm-2).
Preparation of EEBP: EEBP was obtained using electrochemical
exfoliation method. Two electrodes system (BP as cathode and
Pt wire as anode) was served for the expansion of bulk BP at -10
V with the help of small gas bubbles formed from DMSO after 25
min. 30 mL DMSO dissolved with 0.1 M TBAB was used as
electrolyte. And then the sponge-like BP can be further exfoliated
and dispersed via ultrasonication using a biomixer in 6 minutes
with power of 300 W, the working and stop time of 5 s, respectively.
The obtained grey suspension was fully washed at the speed of
10000 rpm for 10 min with ethanol for several times. The
precipitation was collected after dried in a vacuum oven.
Synthesis of MoS2/EEBP nanosheet: 20 mg black phosphorus
nanosheets were dispersed in 36 mL DMF, and 40 mg
(NH4)2MoS4 was added in. After high speed stirring for 30 min and
and sonication for 30 min, the solution was transferred into a 50
ml Teflon stainless-steel autoclave and kept it at 210 ℃ for 15 h.
Once cooling down naturally, the obtained black products were
fully washed at a speed of 6000 rpm for 6 min with ethanol for five
times. Finally, the precipitation was collected after vacuum dried
overnight.
Characterizations: Field emission scanning electron microscope
(FEI Verios 460) was utilized to characterize the morphologies. A
transmission electron microscope (JEM-2100F) with EDS was
adopted to investigate the morphologies, crystal and elements
information. The morphology and thickness of EEBP was
measured from Atom force microscope (AFM) (DIMENSION
IOON) results. The crystalline phase compositions was detected
XRD (PANalytical X'Pert Pro) with a Cu Kα1 radiation source (λ =
1.54056 Å). Horiba HR800 spectrometer (a 532 nm laser as the
excitation source) was used to examine the Raman spectra of
samples. The surface valance state and composition were tested
by XPS (Thermo Fisher Scientific ESCALAB Xi+). A Kruss DSA30
5
This article is protected by copyright. All rights reserved.
10.1002/cctc.202000139
equipment was employed to check the optical contact angle of
samples.
Electrochemical measurements: The catalytic ink is prepared by
dispersing 5 mg catalyst in a mixture of 0.9 mL ethanol, 0.08 mL
ultrapure water and 0.02 mL Nafion. Afterward, 5 µL ink was
placed uniformly on a glass-carbon (GC) electrode (3 mm
diameter) and dried slowly. HER performance in all types of
electrolytes were tested using Autolab PGSTAT204 station. A
conventional 3-electrode set-up (Ag/AgCl reference, graphite rod
counter and GC working electrode) was used to test the HER
activity of samples. The LSV curves were tested at a scan rate of
5 mV s−1 ranging from -0.6 to -0.1 V (vs RHE). The EIS
Accepted Manuscript
measurements were detected within the range from 0.1 Hz to 100
kHz, while the amplitude was set as 5 mV. The CV curves were
examined at -0.8 -0 V range (vs RHE) for 100 cycles. And the
ECSA measurements within the range of -0.054-0.044 V were
examined with scan speed from 20 mV to 120 mV, respectively.
Mott-Schottky plots were also measured with a 3-electrode setup
in 0.5 M Na2SO4 electrolyte.[37]
DFT calculation method: The DFT calculations were done using
projector augmented-wave (PAW) method and the Vienna Ab
Initio Simulation Package (VASP) code.[38] The electronic
exchange-correlation function of the interacting electrons was
studied employing Perdew-Burke-Ernzerhof (PBE) within the
generalized gradient approximation (GGA).[39] Moreover, the van
der Waals interaction was taken into consideration by adopting
the empirical correction in Grimme’s scheme, i.e., DFT+D3.[40]
The energy cutoff is set to 450 eV in this work. In the geometry
optimization and DOS calculation, k-meshes is set as 1×1×1 in
this work. The thickness of vacuum slab is above 20 Å. Between
two consecutive steps, the convergence criterion for the energy
difference was lower than 10-5 eV. On each atom, the Hellmann–
Feynman force was below 0.01 eV Å-1.
Acknowledgements
This work was jointly supported by the National Natural Science
Foundation of China (Grant Nos. 51802252, 61565004 and
61965005), National Science and Technology Major Project
(Grant No. 2017ZX02101007-003), the Natural Science
Foundation of Shaanxi Province (Nos. 2019TD-020 and
2017JZ015), and Project supported by State Key Laboratory for
Powder Metallurgy, Central South University, Changsha. We
thank Miss Liu at Instrument Analysis Center of Xi'an Jiaotong
University for her assistance with XPS analysis. This research
used the resources of the HPCC platform in Xi'an Jiaotong
University.
Keywords: electrochemical exfoliation• black phosphorous •
MoS2 • hydrogen evolution • interface engineering
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Accepted Manuscript

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ChemCatChem 10.1002/cctc.202000139

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Table of Contents

Accepted Manuscript
A uniform and scalable heterostructure is built through in situ formation of MoS2 nanosheets on electro-exfoliated black phosphorus
(EEBP) vertically, presenting the pH-universal catalytic activity for hydrogen evolution reaction with low overpotentials and Tafel slopes.
Both experimental and theoretical study indicate that MoS2-EEBP interface can aggrandize activity sites, benefit the electrons migration
and accelerate the HER process.

8
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