Research Article

ISSN 1998-0124 CN 11-5974/O4

https://doi.org/10.1007/s12274-021-4002-y

Line defects in monolayer TiSe2 with adsorption of Pt atoms

potentially enable excellent catalytic activity
Zhipeng Song1,§,  Juxia Yi1,§,  Jing Qi1,  Qi Zheng1,  Zhili Zhu1,  Lei Tao1,  Yun Cao1,  Yan Li1,  Zhaoyan Gao1,  Ruizi 
✉
Zhang1  ( ),  Li Huang1,  Geng Li1,2,3,  Ziqiang Xu4,  Xu Wu4,  Yeliang Wang4,  Chengmin Shen1,2,  Yu-Yang Zhang1,2,
✉ ✉
Hongliang Lu1,2 ( ), Xiao Lin1,2 ( ), Shixuan Du1,2,3, and Hong-Jun Gao1,2,3
1 
Institute of Physics and University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, China
2 
CAS Center for Excellence in Topological Quantum Computation, Chinese Academy of Sciences, Beijing 100190, China
3 
Songshan Lake Materials Laboratory, Dongguan 523808, China
4 
School of Information and Electronics, Beijing Institute of Technology, Beijing 100081, China
§
Zhipeng Song and Juxia Yi contributed equally to this work.
 

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
Received: 26 September 2021 / Revised: 12 November 2021 / Accepted: 16 November 2021

ABSTRACT
Two-dimensional (2D) materials with defects are desired for catalysis after the adsorption of monodispersed noble metal atoms.
High-performance catalysts with the absolute value of Gibbs free energy (|ΔGH|) close to zero, is one of the ultimate goals in the
catalytic  field.  Here,  we  report  the  formation  of  monolayer  titanium  selenide  (TiSe2)  with  line  defects.  The  low-temperature
scanning  tunneling  microscopy/spectroscopy  (STM/S)  measurements  revealed  the  structure  and  electronic  states  of  the  line
defect.  Density  functional  theory  (DFT)  calculation  results  confirmed  that  the  line  defects  were  induced  by  selenium  vacancies
and  the  STM  simulation  was  in  good  agreement  with  the  experimental  results.  Further,  DFT  calculations  show  that  monolayer
TiSe2 with line defects have good catalytic activity for hydrogen evolution reaction (HER). If the defects are decorated with single
Pt atom, the HER catalytic activity will be enhanced dramatically (|ΔGH| = 0.006 eV), which is much better than Pt metal (|ΔGH| =
0.09 eV). Line defects in monolayer TiSe2/Au(111) provide a wonderful platform for the design of high-performance catalysts.

KEYWORDS
line  defects,  hydrogen  evolution  reaction,  monolayer  titanium  selenide  (TiSe2),  scanning  tunneling  microscope,  density
functional theory calculation
 
 

1    Introduction
Properties of materials are highly sensitive to the emergence of
defects. Two-dimensional (2D) transition metal dichalcogenides
(TMDs) are attracting much attention due to their rich properties,
including different types of bandgaps [1–5], charge density
wave [6, 7], extraordinary superconducting phenomenon [8, 9],
quantum spin Hall effect [10], and a wide range of potential
applications in novel devices [11–14]. Correspondingly, the defects
in 2D TMDs are expected to introduce fascinating properties.
Point defects in 2D TMDs can modulate charge transport [15]
and generate ferromagnetism [16], whereas line defects may
introduce extraordinary optical [17], electronic [18], and magnetic
properties [19]. Several types of line defects have been theoretically
proposed and experimentally fabricated such as grain boundaries
or irregular defects [20, 21]. Searching for new types of line defects
in TMDs, revealing the defect structure, and its influence on the
properties of 2D materials are essential to the applications of these
materials.
TMDs are widely regarded as the ideal catalysts for hydrogen
evolution reaction (HER) due to their large specific surface area
and unique physicochemical properties [22–26]. However,
catalytic activity of pristine TMDs is still lower than Pt and its
alloys (the most efficient catalysts for HER so far) [27, 28]. Defect
engineering is one of the major strategies to enhance catalytic
activity of TMDs for HER. The absolute value of Gibbs free energy
(|ΔGH|) is an important indication for evaluating the HER activity.
A smaller |ΔGH| denotes a strong binding of protons and surface,
whereas a larger |ΔGH| represents H atoms are hard to be
absorbed on the catalytic surface, indicating an ideal value of
|ΔGH| at the vicinity of zero (|ΔGH| ≈ 0) [29]. Compared with the
pristine monolayer MX2 (M = Mo, W, or V and X = S, Se, or Te),
MX2 with defects shows an obviously lower |ΔGH|. For example,
the |ΔGH| of the pristine VSe2 is ~ 0.31 eV [30], whereas the |ΔGH|
decreases to 0.15 eV when Se vacancies are introduced [27]. Given
the relatively high catalytic activity of Pt and defective TMDs, it is
an interesting question whether one can achieve better catalytic
activity by combing the two materials.
Here, we employed molecular beam epitaxy to fabricate
monolayer TiSe2 with line defects on Au(111) substrate. By
combining scanning tunneling microscopy (STM), low-energy
electron diffraction (LEED) characterizations , and density
functional theory (DFT) calculation, we reveal the structure of
monolayer TiSe2 with line defects. Scanning tunneling
spectroscopy (STS) investigations exhibit distinct electronic state
near the line defect. DFT calculations indicate catalytic activity for

Address correspondence to Ruizi Zhang, zhangrz@iphy.ac.cn; Hongliang Lu, luhl@ucas.ac.cn; Xiao Lin, xlin@ucas.ac.cn

2 Nano Res.
HER in monolayer TiSe2 with such line defects, and further
predict the adsorption of single Pt atom on the line defects can
enhance the catalytic activity dramatically.
2    Methods
2.1    Experimental
Monolayer TiSe2 was grown on Au(111) substrate in an ultra-high
vacuum molecular beam epitaxy (MBE) system with a base
pressure better than 3 × 10−10 mbar. Firstly, the Au(111) surface
was cleaned by several cycles of argon-ion sputtering and
annealing until the sharp diffraction spots were shown in a LEED
pattern and atomically resolved STM images were observed. Then,
high purity Se (99.99%) and Ti (99.9%) were successively
deposited on Au(111) at a substrate temperature of 300 K. Finally,
the sample was heated to 600 K to form monolayer TiSe2 with line
defects. The schematic illustration of the growth process is shown
in Fig. 1(a). STM measurements were performed at a base
pressure of ~ 2 × 10−10 mbar and the electron energy used in LEED
experiment was 53 eV.
2.2    Calculational
All calculations based on DFT are performed using the Vienna ab
initio simulation package (VASP) [31, 32]. The projector
augmented wave (PAW) [33] potential was employed to describe
the core electrons, and the Perdew–Burke–Ernzerhof (PBE) [34]
version of the generalized gradient approximation (GGA) [35] was
used for electronic exchange-correlation interaction. A dispersion
correction of total energy (DFT-D3 method of Grimme) [36] was
used to incorporate the van der Waals interaction in the system.
The periodic slab models of TiSe2/Au(111) include 4 × 4
monolayer TiSe2 and 5 × 5 Au(111) substrate, in which four layers
of Au(111) substrate were chosen and the bottom two layers were
fixed in the geometry optimization. A vacuum slab of larger than
15 Å was selected to avoid interactions between neighboring
(a)
Au(111)
Annealing
Au(111)
(c) 2p3/2
Ti
2p1/2
Figure 1    (a) Schematic illustrations of the growth process of monolayer TiSe2 on Au(111). (b) LEED pattern of the sample at 300 K, showing diffraction spots from
Au(111) substrate (yellow arrow), TiSe2 (blue arrow), and moiré pattern (white arrow). (c) and (d) XPS of the Ti 2p and Se 3d core levels. The blue and red curves are
fitting curves corresponding to the Se 3d core levels from Se cluster on Au(111) and TiSe2, respectively. The orange points represent the raw data and the black line is
the fitting line.
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supercells. The electronic wave functions were expanded in plane
waves with a kinetic energy cutoff of 500 eV. The first Brillouin
zone was sampled with only the Γ-points. The structures were
relaxed until the energy and residual force on each atom were
smaller than 10−5 eV and 0.01 eV·Å−1, respectively. The STM
simulations were performed using the Tersoff-Hamann approach
[37]. The Gibbs free energy of hydrogen adsorption, ΔGH, is
calculated as ΔGH = ΔEH + ΔEZPE − TΔSH, where ΔEH is the
binding energy of adsorbed hydrogen, ΔEZPE and ΔSH are the zero-
point energy difference and entropy difference between the
adsorbed hydrogen and hydrogen in the gas phase, respectively. In
the standard condition, ΔEZPE − TΔSH is 0.24 eV, which is widely
accepted [38].
3    Results and discussion
The structure of TiSe2 on the Au(111) substrate can be confirmed
by LEED, as shown in Fig. 1(b). The outermost six diffraction
spots, one of which is highlighted by the yellow arrow, originate
from the Au(111) substrate with six-fold symmetry. The inner six
diffraction spots (marked by the blue arrow) are assigned to the
TiSe2 lattice, and other sets of spots (marked by the white arrow)
are induced by the moiré pattern. The lattice constant of the film
(0.35 nm) can be determined from LEED according to the
Au(111) lattice constant (0.29 nm), which is consistent with the
lattice constant of TiSe2 [39]. These clear and sharp diffraction
spots were observed on the entire sample, indicating the formation
of a high-quality TiSe2 film. X-ray photoelectron spectroscopy
(XPS) measurement was performed to study the chemical state of
the sample (Figs. 1(c) and 1(d)). The XPS peaks located at 461.7
and 455.5 eV in Fig. 1(c) are consistent with Ti 2p1/2 and 2p3/2 in
TiSe2 [40]. The XPS spectrum (Se 2p) can be fitted with two pairs
of peaks. The two red peaks at 54.2 and 53.2 eV in Fig. 1(d)
correspond to Se 3d3/2 and 3d5/2 core levels in TiSe2 [40], while the
two blue peaks located at 54.6 and 53.6 eV are from Se 3d3/2 and
3d5/2 in Se clusters, respectively. Combining LEED and XPS
characterizations, we confirmed that the film is TiSe2.
Ti
(b)
Se
TiSe2
TiSe2
Moiré pattern
Au
(d) Se
3d3/2
3d5/2
Se cluster
Se2−
Nano Res.
To investigate the surface morphology of the TiSe2, we
performed STM characterization. A large-scale STM image is
shown in Fig. 2(a), which exhibits a flat film. We can clearly see
that the monolayer TiSe2 on the Au(111) substrate is not a
complete and continuous film, but consists of triangular domains
with line defects. In addition, there are small clusters of Se on the
Au(111) substrate. There are several possible reasons for the
formation of line defects in 2D materials, including formation of
line defects between different structural phases [41] or different
crystal orientations [42], spontaneous formation of line
defects [43], and post-treatment [44]. For the line defects in
TiSe2/Au(111) here, the structural phases and crystal orientations
of materials on both sides are consistent, and the line defects were
already present after the sample was prepared. Therefore, we think
that the line defects in TiSe2 formed spontaneously due to growth
process imperfections−the deviation of stoichiometric ratio
occurred at the junction due to the stress or other reasons, making
it difficult for Se to participate in the reaction, thus creating
defects. Figure 2(b) shows an atomically resolved image of the area
indicated by the blue square in Fig. 2(a), revealing well-ordered
moiré superstructures. The atomic-resolution STM image shows a
triangular arrangement of atoms with the lattice constant of ~ 0.35
nm, which agrees with the previously reported lattice constant of
monolayer TiSe2 [39]. It is apparent that the orientations of the
moiré superstructure (the unit cell is marked by the black
rhombus) are aligned with TiSe2 lattice, and the lattice constant of
the moiré superstructure is amoiré ≈ 1.50 nm, which is about four
times of that of TiSe2 and is in good agreement with the LEED
pattern. In order to understand the structure of monolayer TiSe2
on Au(111) substrate, we carried out DFT calculations. Figure 2(c)
shows the optimized atomic structure of TiSe2/Au(111). In the top
view, we found that both the orientations and the periodicity of
the moiré superstructure agree well with the experimental image.
In the side view, the height of monolayer TiSe2 on Au(111) surface
is 5.5 Å in the optimized atomic structure, which is higher than
the experimental data. It may be due to Se clusters surrounding
TiSe2 islands in the sample and different conductive properties
(a)
20 nm
(c)
Se
Ti
Au
Figure 2    (a) Large-scale STM image of monolayer TiSe2 grown on Au(111) (Vs = −1.4 V, Is = 50 pA). (b) High-resolution STM image of monolayer TiSe2 in the blue
square in (a) (Vs = −0.5 V, Is = 500 pA). (c) Top view and side view of atomic model of DFT optimized monolayer TiSe2 on Au(111) substrate. (d) STM simulation
based on the calculated structure in (c). The black rhombuses in (b)–(d) indicate the unit cells of the moiré pattern.
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3
between TiSe2 and Au(111). This phenomenon is similar to MoSe2
on Au(111) [45]. The corresponding STM simulation, as shown in
Fig. 2(d), agrees well with the experimental image in Fig. 2(b).
In Fig. 2(a), three different orientations of the line defects can
be seen, and we chose a representative one in the vertical direction
for a small range STM characterization, as shown in Fig. 3(a).
STM image in this scale clearly shows the line defect, moiré
superstructures, and atomic resolution of TiSe2. Figure 3(b) shows
a close-up STM image of the line defect in TiSe2. In order to clarify
the structure of the line defect, DFT calculations were carried out.
Figure 3(c) shows the optimized atomic structure close to line
defect in TiSe2/Au(111), and Fig. 3(d) shows the corresponding
STM simulation image, which is in good agreement with the
experimental image (Fig. 3(b)). Combining the experimental STM
image and calculation results, we confirmed that the line defect
originates from the absence of a column of selenium atoms in the
top layer of TiSe2. To investigate the electronic properties of TiSe2
near the defect, we measured STS spectra at eight positions along
the white dots in Fig. 3(a). The dI/dV curves in the range of
0–1 eV change obviously from position 1 to 8, as shown in
Fig. 3(e). Spectra 1 and 2 of the black lines were acquired far from
the line defect and can be seen as the intrinsic STS spectrum of
TiSe2/Au(111). There is a significant change from spectrum 3 of
the blue line, especially from spectra 4 and 5, where an obvious
new peak appears near 0.5 eV. This indicates that a defect state is
generated from position 3, which is about 2 nm away from the
line defect. Spectra 6 and 7 are very similar to spectrum 8, because
they were measured at positions very close to the line defect.
Figure 3(f) shows the STS spectra in a wider energy range for three
representative positions. It can be seen that the line defect can
affect the electronic structure of its nearby region.
TMDs can be used as catalysts or templates for
catalysis [42, 43]. Here, we explored the HER catalytic
performance of monolayer TiSe2 on the Au(111) substrate via
|ΔGH| calculation. As shown in Fig. 4(i), the |ΔGH| of the pristine
monolayer TiSe2 on the Au(111) substrate (Fig. 2(c)) is 0.640 eV,
which indicates it is an inefficient HER catalyst. Meanwhile, the
(b)
1 nm
(d)
4 Nano Res.
 
 

(a) (c) (e)

8
7
6

dI/dV (a.u.)
5
4
8 3
5 2
1
1
2 nm

(b) (d) (f)

8

dI/dV (a.u.)
5

11 nm
nm

Figure 3    (a) STM image shows a line defect in TiSe2/Au(111). (Vs = −0.5 V, Is = 500 pA). (b) Atomically resolved STM image of the line defect. The scanning
parameters are the same to (a). (c) The atomic model of DFT optimized line defect in monolayer TiSe2 on Au(111) substrate. (d) STM simulation based on the
calculated structure in (c). (e) STS spectra near the line defect as indicated by the white dots in (a). (f) Representative spectra of three points close to the line defect in
TiSe2/Au(111). The black rhombuses in (b)–(d) indicate the unit cells of the moiré pattern.

|ΔGH| of monolayer TiSe2 with line defects on the Au(111)
substrate (Fig. 3(c)) is 0.107 eV, which is comparable to the |ΔGH|
of Pt metal surface (0.090 eV) [38]. It indicates that the line defects
indeed modulate the chemical properties of monolayer TiSe2 on
Au(111) substrate, and monolayer TiSe2 with line defects has the
potential to be a good HER catalyst.
Furthermore, the line defect in 2D materials is an ideal platform
which provides suitable adsorption sites for single-atom catalysts
(SAC). In order to demonstrate the stability of Pt atoms on the
line defect of TiSe2, Pt atoms were deposited on the defect by
electron-beam evaporation in an ultra-high vacuum chamber.
STM images show that the Pt atoms can be stably adsorbed on the
defect (Figs 4(a)–4(c)). Here, we investigated the catalytic activity
of the line defects in monolayer TiSe2 with Pt adatoms. Different
numbers of adsorbed Pt atoms were considered at first, as shown
in Figs. 4(d)–4(g). Furthermore, DFT calculations show the
adsorption energy per Pt adatom for single Pt adatom is −0.362
eV, which is the largest one in all configurations we are able to
study. As shown in Fig. 4(h), the adsorption energy per Pt adatom
increases from −0.362 to −0.157 eV with the increase of Pt
adatoms. Therefore, the Pt adatoms tend to form monodisperse
adsorption on the monolayer TiSe2 with line defects on the
Au(111) substrate.
To further investigate the HER catalytic activity of the line
defects in TiSe2 with Pt adatoms, the |ΔGH| of Pt adatoms in
different configurations were calculated, as shown in Fig. 4(i). The
|ΔGH| of the structure with single Pt adatom is 0.006 eV, while the
|ΔGH| of the structures with Pt dimer and Pt trimer adatoms are
0.010 and 0.019 eV, respectively. The |ΔGH| increased to
0.073 eV when the Se-deficient line defects were fully occupied by
Pt adatoms. The small value of |ΔGH| in the line defects in TiSe2
with Pt adatoms indicates that it will exhibit excellent HER

(a) (b) (c)

 

5Å 5Å 5Å

(d) (e) (f) (g) Se

Ti
Au
Pt

(h) (i)

Figure 4    (a)–(c) STM images of the single Pt adatom, Pt dimer, and more Pt adatoms adsorbed on the line defect at 300 K, respectively. The scanning parameters are
VS = −1 V, IS = 0.2 nA in (a), and VS = −0.2 V, IS = 0.2 nA in (b) and (c), respectively. (d)–(g) Atomic models of TiSe2/Au(111) with single Pt adatom, Pt dimer, Pt
trimer, and more Pt adatoms adsorbed on the line defect, respectively. (h) Adsorption energy per Pt adatom in configurations with different numbers of Pt adatoms
adsorbed on the line defect in TiSe2/Au(111). (i) Calculated absolute value of Gibbs free energy (|ΔGH|) for atomic hydrogen adsorption on pristine TiSe2 (Fig. 2(c)),
line defect in TiSe2 (Fig. 3(c)) and Pt adatoms in different configurations (4(d)–4(g)), compared with the |ΔGH| of Pt metal [38].
 

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Nano Res.
catalytic activity. Therefore, the construction of such line defects in
TiSe2 provides a suitable platform for selective adsorption of Pt
adatoms, which has promising applications in HER catalysis.
For the practical applications of TMDs as catalysts, it was
reported that electrochemical testing for HER using Pt
nanoparticles decorated edge-enriched MoS2 as working electrode
can be performed in a 0.5 M H2SO4 Ar-purged solution [46]. The
HER performance of VSe2 quantum dots can also be evaluated
experimentally by the standard three-electrode configuration in a
0.5 M H2SO4 electrolyte [47]. The practical applications of TiSe2 as
catalysts may be realized by transferring the sample to some acid
solution in an atmosphere of inert gases (e.g., nitrogen or argon)
to avoid oxidation. The great potential of using this material as
catalysts deserves more further research to solve the stability
problem in practical applications.
4    Conclusions
In summary, monolayer TiSe2 with line defects were successfully
fabricated on the Au(111) substrate. STM characterization and
DFT calculation confirmed that the defects were induced by the
absence of a column of top Se atoms in TiSe2. We experimentally
observed an obvious defect state by measuring the dI/dV spectra
close to the line defect. Furthermore, the DFT calculations shows
that the line defect itself has catalytic activity for HER, and it will
have better catalytic activity if it adsorbs Pt atoms. It was found
that the line defect with monodispersed Pt atoms shows excellent
HER catalytic activity. This work enriches the structure of line
defects in TMDs and shows potential applications of such defects
in catalysis.
Acknowledgments
We thank Guangchao Chen for his help. This work was supported
by the National Key R&D Program of China (Nos.
2019YFA0308500 and 2018YFA0305800), the National Natural
Science Foundation of China (Nos. 61925111 and 61888102),
Strategic Priority Research Program of Chinese Academy of
Sciences (Nos. XDB28000000 and XDB30000000), the
Fundamental Research Funds for the Central Universities, and
CAS Key Laboratory of Vacuum Physics.
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