Applied Surface Science 500 (2020) 144248

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Applied Surface Science

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Two-dimensional chromium boride MBenes with high HER catalytic activity T

a a,⁎ b a a,⁎
Bikun Zhang , Jian Zhou , Zhonglu Guo , Qiong Peng , Zhimei Sun
a
School of Materials Science and Engineering & Centre for Integrated Computational Materials Science, International Research Institute for Multidisciplinary Science,
Beihang University, Beijing 100191, China
b
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China

A R T I C LE I N FO A B S T R A C T

Keywords: Facing the increasing demands of clean energy, searching low-cost and highly active catalysts of hydrogen
First-principles calculation evolution reactions (HER) has emerged as a major task. Herein on the basis of density functional theory cal-
Two-dimensional materials culations, we reported that a series of Cr-based MBenes of different atomic-layer thickness (referring to 2D
MBenes transition metal borides), Crn+1B2n (n = 1–3), exhibit superior electrocatalytic performance towards HER. They
Hydrogen evolution reaction
are highly stable, mechanical anisotropic and intrinsic ferromagnetic conductive systems. Furthermore, we
Electrocatalysis
found that they show thickness-dependent mechanical properties and HER catalytic activity. Especially, Cr4B6
exhibits quite high Young’s module of 335 N/m (comparable to 342 N/m of graphene) and 247 N/m along x and
y axes, respectively. More importantly, Cr4B6 is identified as a superior HER electrocatalyst with overpotential of
only 0.003 V at H coverage of 1 monolayer (ML), which is a promising alternative of Pt catalyst.

1. Introduction transition metal borides, known as MBenes, could be obtained

H2 is one of the most important clean and sustainable energy re-
sources [1]. As a key step to electrochemically produce H2, the effi-
ciency of hydrogen evolution reaction (HER) is strongly dependent on
the eletrocatalysts. Pt is the most widely used electrocatalyst nowadays,
but its high cost and scarcity hinder the commercial application.
Therefore, exploring non-precious alternatives of Pt has been a hot
research topic for decades [2–9]. Two-dimensional (2D) materials have
received considerable attention in recent years due to their large spe-
cific surface area. Among them, 2D transition metal carbides/nitrides/
carbonitrides, known as MXenes, have been widely studied both ex-
perimentally and theoretically [2,3,5,8,10–21]. MXenes could be syn-
thesized by removing the A (A represents Al in most cases) atomic
layers in MAX phases experimentally, where M is transition metal and X
is C or N. In recent years, MXenes are widely studied as HER catalysts,
due to their metallic nature, multiple active sites and high HER catalytic
activity [2,3,5,8,19–21]. However, during the preparation process,
MXenes are inevitably functionalized with mixed terminations such as
F, Cl, O and OH, leading to uncontrollable atomic composition.
Therefore, it is urgent to search component-controllable 2D materials
with high catalytic activity.
MAB phases, analogous to MAX phases, are layered bulk phases
with the sequence of transition metal atoms, A atoms (Al or In) and B
atoms [22–25]. By removing the A atomic layers, a new type of 2D
[9,25–29]. Up to now, 2D Mo2B2 [28], Cr2B2 [26] and Ti2B2 [25] have
been synthesized experimentally. Notably, no terminations were ob-
served, indicating that the components of MBenes could be accurately
controlled. According to the previous works [9,25,27], MBenes are all
metallic with good conductivity, which is one of the most significant
factors for electrocatalysts. However, the reported MBenes so far are all
M2B2-type, which limits the richness of MBenes. Inspired by the fact
that Ti3C2O2 and Nb4C3O2 MXenes exhibit high HER activity [8], it is of
significance to investigate the multi-thickness MBenes to provide fun-
damental understanding of their electrocatalytic performance.
Therefore, in this work, we report a series of Cr-based MBenes with
different atomic-layer thickness, labeled as Crn+1B2n (n = 1–3), and
reveal their HER catalytic activity by means of ab initio calculations.
These Cr-based MBenes show good structural stability, metallic con-
ductivity as well as thickness-dependent high Young’s module and HER
catalytic activity. In particular, Cr4B6 exhibit great comprehensive po-
tential of HER catalysis compared to MXenes.
2. Computational details
In this work, ab initio calculations based on density functional
theory (DFT) was performed by using Vienna Ab initio Simulation
Package (VASP) [30,31]. The projector augmented wave (PAW) [32]
method and generalized gradient approximation (GGA) of

⁎
Corresponding authors.
E-mail addresses: jzhou@buaa.edu.cn (J. Zhou), zmsun@buaa.edu.cn (Z. Sun).

https://doi.org/10.1016/j.apsusc.2019.144248
Received 24 July 2019; Received in revised form 27 August 2019; Accepted 30 September 2019
Available online 08 October 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
B. Zhang, et al.
Fig. 1. Crystal structures of (a) Cr2AlB2, Cr3AlB4 and Cr4AlB6; (b) Crystal structures from the top view for Crn+1B2n and the side view for Cr2B2, Cr3B4 and Cr4B6,
respectively.
Fig. 2. Phonon dispersion curves of Cr2B2, Cr3B4 and Cr4B6.
Perdew–Burke–Ernzerhof (PBE) [33] were used to describe ion-electron
interaction and electron exchange-correlation, respectively. We treated
the electrons of Cr-3p63d54s1, B-2s22p1 and H-1s1 orbitals as valence
electrons. Considering the strongly correlated Cr-3d electrons, we used
GGA + U method [34] to study the magnetic and electronic properties
of Crn+1B2n. The effective value of U was set to 4 eV for Cr2B2 and
3.5 eV for Cr3B4 and Cr4B6, which were carefully tested by comparing
the calculation results and experimental results[24] of the lattice con-
stants and cell volumes of Crn+1AlB2n based on the previous works
[35,36]. All the structures were fully relaxed with the tolerance of 10−6
eV in energy and a 16 × 16 × 1 Monkhorst-Pack k-point grid. Vacuum
layers more than 15 Å was adopted to avoid the interaction between
neighboring MBene slabs. Density-functional perturbation theory [37]
method was used to calculate the force constants in the phonon dis-
persion calculation by Phonopy program. The calculation details of
interface separation energy, elastic constants and free energy of H ad-
sorption are included in the supplementary information.
3. Results and discussion
As the precursors of 2D Crn+1B2n, Cr2AlB2, Cr4AlB6 belong to Cmma
space group (No.65) while Cr3AlB4 belongs to Pmmm space group
(No.47). All the three bulk phases are conductive according to both the
previous experimental work [23] and our calculation. As shown in
Fig. 1(a), Crn+1AlB2n are formed by alternating stacking of Al atomic
2
Applied Surface Science 500 (2020) 144248
layers and Crn+1B2n layers. Considering the similarity between MAB
and MAX phases, the Cr-based MBenes are expected to be synthesized in
the same way as MXenes. To evaluate the feasibility of removing Al
atomic layers from MAB phases, we investigated the difference of in-
terface separation energy between Cr/B and Cr/Al interfaces. As illu-
strated in Fig. S1, it is clear that the separation energy of Cr/B interface
is about twice higher than that of Cr/Al interfaces for Crn+1AlB2n, in-
dicating that CreB bonds are much stronger than CreAl bonds.
Therefore, Crn+1B2n are expected to be synthesized by selective che-
mical etching, which is the most commonly used method to synthesize
MXenes and has been applied to the synthesis of 2D Cr2B2 [9] and
Mo2B2 [28,29]. By removing Al atomic layers from Crn+1AlB2n, we can
obtain 2D Crn+1B2n, as shown in Fig. 1(b). The three Cr-based MBenes
are all orthorhombic and the zigzag diatomic B layers are sandwiched
by flat Cr atomic layers, which are different from Cr-based MXenes
[38].
To examine the stability of Crn+1B2n, firstly we calculated their
cohesive energy by Eq. (1),
nECr + 2nEB − ECrn + 1 B2n
Ec =
3n + 1 (1)
where ECrn + 1 B2n , ECr and EB are the total energy of Crn+1B2n, isolated Cr
atom and isolated B atom, respectively. The cohesive energy of Cr2B2,
Cr3B4 and Cr4B6 is calculated to be 6.30 eV, 6.43 eV and 6.48 eV per
atom, respectively. The positive cohesive energy suggests that they are
B. Zhang, et al. Applied Surface Science 500 (2020) 144248

Fig. 3. Spin density maps of (a) Crn+1B2n and electronic structures of (b) Cr2B2, (c) Cr3B4 and (d) Cr4B6. The spin-polarized PDOS, band structure of majority and
minority spins are shown in the middle, left and right panels, respectively.

stable. Then we studied their phonon dispersion. As shown in Fig. 2,
there is no imaginary frequency for Crn+1B2n, suggesting that they are
dynamically stable [39]. Besides, the maximum frequencies are more
than 800 cm−1, suggesting strong chemical bonding in the three
MBenes. Also, we calculated the elastic constants of Crn+1B2n and the
corresponding results are listed in Table S3. Apparently, Crn+1B2n sa-
2
tisfy the Born criteria (c11 > 0, c11 c22 > c12 , c44 > 0 ) [40], indicating that
they are mechanically stable.

3
B. Zhang, et al.
Fig. 4. Strain-stress curve of Crn+1B2n. The inset shows the fitted linear relationships between strain and stress from 0 to 4%, in which the Young’s module is
obtained.
Fig. 5. HER volcano curve of Crn+1B2n (stars) compared with some previously
reported MXenes from Ref. [3] and Ref. [5] (blue and green symbols) and
MBenes from Ref. [9] (pink symbols) at H coverage of 1/4 ML. The systems
with overpotentials below 0.2 V are located in the yellow shaded area. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
To determine the magnetic ground states of Cr2B2, Cr3B4 and Cr4B6,
we constructed several magnetic configurations (one ferromagnetic
(FM) and three antiferromagnetic (AFM) for both Cr2B2 and Cr3B4,
while one ferromagnetic (FM) and three antiferromagnetic (AFM) for
Cr4B6), as shown in Fig. S2, and compared their total energies based on
2 × 2 supercells. It is seen in Table S4 that the total energy of FM
Fig. 6. The Gibbs free energy diagram of HER at different H coverages (1/4, 1/2, 3/4 and 1 ML) on the surface of (a) Cr2B2, (b) Cr3B4 and (c) Cr4B6. The red balls in
the insets represent H atoms. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
4
Applied Surface Science 500 (2020) 144248
configurations is more negative than that of AFM configurations by
1.78 eV, 0.91 eV and 0.03 eV for Cr2B2, Cr3B4 and Cr4B6, respectively,
implying that Crn+1B2n are all ferromagnetic 2D materials. Their total
magnetic moments are 6.1 μB, 6.7 μB and 10.0 μB per unit cell for
Cr2B2, Cr3B4 and Cr4B6, respectively, mainly contributed by the Cr
atoms, which could be clearly seen from the spin density maps, as
shown in Fig. 3. Possessing strong magnetic moments, Crn+1B2n are
expected to be applied as spintronic devices.
Based on the ferromagnetic configurations of Crn+1B2n, we con-
ducted the subsequent research on their electronic properties by ana-
lyzing their electronic structures including band structures, total den-
sity of states (TDOS) and projected density of states (PDOS) as shown in
Fig. 3. It is obvious that Cr2B2, Cr3B4 and Cr4B6 are all metallic with
several bands crossing the Fermi levels in both spin-up and spin-down
channels. The middle panels of Fig. 3 depict the PDOS of Crn+1B2n.
Notably, there is significant hybridization between Cr-3d and B-2p or-
bitals in the ranges of −1 ~ −3 eV for Cr2B2 and −2 ~ −3 eV for
Cr3B4 and −1.5 ~ −3 eV for Cr4B6 in the spin-down channels, showing
strong interaction between Cr and B atoms. From the PDOS near the
Fermi levels, it is clear that the metallic character is predominantly
contributed by the 3d electrons of Cr atoms while the 2p electrons of B
atoms make little contribution to the Fermi levels in all three systems.
Besides, we noticed that near the Fermi levels, the density of states of
spin-up channels are higher than spin-down channels, which indicates
that the metallic nature of Crn+1B2n mainly attributes to their spin-up
channels. The metallic character of Crn+1B2n results in their excellent
electronic conductivity, which provides advantages in the application
of HER catalysts.
In practical application, 2D materials are prone to be stressed.
Therefore, we studied mechanical properties of Crn+1B2n. The strain-
stress curves are shown in Fig. 4. By linearly fitting the relationship of
B. Zhang, et al.
stress and strain up to 4%, we obtain their Young’s module, which in-
creases with atomic-layer thickness along both x and y axes. Notably,
Young’s module along y axis (Ey) is larger than that of x axis (Ex) for
Crn+1B2n, indicating their mechanical anisotropy. The Ex and Ey of
Cr4B6 are as high as 335 N/m and 247 N/m, comparable with graphene
[41] (342 N/m) and h-BN [42](318 N/m), significantly higher than
Ti2C (139 N/m) and MoS2 (129 N/m) [9]. Besides, the ideal strength of
Cr4B6 is about 40.7 and 41.6 N/m with strain of 28% and 36% along x
and y axes, respectively. The excellent mechanical properties provide
assurance of durability during HER application.
HER contains two steps: adsorption of H+ (Volmer reaction:
H + e− → H ∗) and desorption of intermediate adsorbed H* (Tafel re-
+ great HER catalytic activity. We found that they are structural stable,
action: H ∗ + H ∗ → H2 or Heyrovsky reaction: H+ + e− + H ∗ → H2 )
[5,6,8]. The Gibb free energy of the overall reaction is zero, so the
Gibbs free energy of hydrogen adsorption (ΔGH ) is the key descriptor to
evaluate the activity of HER catalysts. Obviously better HER catalytic
performance requires small absolute value of ΔGH or overpotentials (η)
|ΔG |
of HER (η = eH ) [21], which implys small energy barrier of HER. In
general, catalysts with overpotentials smaller than 0.2 V
(|ΔGH | < 0.2 eV) are considered to be HER active [3,5].
HER catalytic activity of Crn+1B2n was studied based on 2 × 2 su-
percell models by calculating their value of ΔGH . Firstly, several pos-
sible adsorption sites of H atom were tested in Fig. S3. By comparing the
H adsorption energy, it is found that H atom tends to adsorb on the site
2, i.e., the top site of the Cr atom of the lower layers. Then the value of
ΔGH under low H coverage (1/4 ML) was calculated to be −0.198 eV,
−0.178 eV and −0.078 eV for Cr2B2, Cr3B4 and Cr4B6, respectively, all
of which show HER catalytic activity and Cr4B6 are even more active
than Pt (0.09 eV) [2–9]. Then a volcano curve (shown in Fig. 5) is
plotted to compare the HER catalytic activity between Crn+1B2n and
some typical MXenes [3,5] and reported MBenes [9]. The closer their
value is to the top of volcano curve, the higher activity the catalysts
have. As shown in the yellow circle in Fig. 5, obviously, the HER cat-
alytic activity of Cr2B2 and Cr3B4 are comparable to that of Nb2CO2,
Ti2NO2 and Nb2NO2 while other considered MXenes are inert. Espe-
cially, Cr4B6 is better than all of them and comparable to Fe2B2, which
is the best of all considered 2D systems [9].
Since Crn+1B2n are active for HER catalysis at low H coverage, we
further studied their HER catalytic activity at higher H coverages from
1/2 to 1 ML based on 2 × 2 supercells. We plotted free energy diagrams
of HER processing under different H coverages, as displayed in Fig. 6.
Cr2B2 gets inert at higher H coverages with too negative value of ΔGH ,
indicating too strong interaction between Cr atoms and H atoms, which
hinders the desorption of intermediate adsorbed H*. In the case of
Cr3B4, at H coverage of 3/4 ML, the absolute value of ΔGH becomes as
small as 0.046 eV, even smaller than Pt, while the value of ΔGH gets too
negative at other H coverages. Surprisingly, Cr4B6 exhibits near-zero
|ΔGH | at all considered H coverages with ΔGH of −0.129 eV, 0.099 eV
and −0.003 eV when H coverages are 1/2, 3/4 and 1 ML, respectively.
Notably, when covered with a whole layer of H atoms on the surface,
Cr4B6 exhibits extremely high HER catalytic activity which is much
better than Pt.
It can be seen that with increasing of the thickness of Crn+1B2n, the
catalytic activity gets higher. According to our calculations, the value of
ΔEZPE − T ΔSH in eq S3 for all three Crn+1B2n is 0.28 eV. Therefore, the
value of ΔGH depends only on hydrogen adsorption energy, ΔEH .
Consequently, too negative or too positive value of ΔEH would lead to
low HER catalytic activity. However, the value of ΔGH for all three
Crn+1B2n at most H coverages is smaller than 0 eV. Thus, the enhanced
HER catalytic activity for thicker Crn+1B2n is due to that the hydrogen
adsorption gets weaker with increasing of the thickness of Crn+1B2n,
leading to less negative value of ΔEH and smaller ΔGH . To further study
the mechanism of hydrogen adsorption, we performed Bader charge
analysis to study the interaction between Cr and H atoms. According to
the results listed in Table S5, we found that at each H coverage, the
5
Applied Surface Science 500 (2020) 144248
thicker is Crn+1B2n, the less electron H atoms gains from Cr atoms,
corresponding to weaker Cr-H interaction. Therefore, in Cr4B6, H atoms
interact with Cr atoms more slightly than in Cr2B2 and Cr3B4. As a re-
sult, the hydrogen desorption is easier for Cr4B6 with relatively less
negative value of ΔEH than Cr2B2 and Cr3B4 and thus has higher HER
catalytic activity.
4. Conclusion
In summary, by using DFT calculations, we reported a series of Cr-
based MBenes with the formula of Crn+1B2n (n = 1–3), which possess
conductive, ferromagnetic and possible to be synthesized from bulk
Crn+1AlB2n (n = 1–3). We discovered that with increasing of thickness,
their Young’s module and HER catalytic activity get higher. Cr4B6 ex-
hibits ultrahigh Young’s module of 335 N/m and 247 N/m along x and y
axes. As for application of HER catalysis, its overpotential reaches as
small as 0.003 V at H coverage of 1ML, which is much smaller than Pt.
Considering their good catalytic activity, conductivity, as well as me-
chanical durability, Crn+1B2n(n = 1–3), especially Cr4B6, are expected
to serve as outstanding HER catalysts. Our work not only expands the
family of MBenes, but also offers highly promising HER electrocatalysts.
However, few MBenes have been synthesized up till now. Therefore, we
expect that more MBenes could be discovered and fabricated to enrich
the world of 2D materials in the future.
Acknowledgments
This work is financially supported by the National Key Research and
Development Program of China (No. 2017YFB0701700) and National
Natural Science Foundation of China (No. 51871009).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.144248.
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