Frontiers of Physics Front. Phys.

https://doi.org/10.1007/s11467-019-0884-5 14(3), 33403 (2019)

Review article

Review of borophene and its potential applications

Zhi-Qiang Wang1,2 , Tie-Yu Lü1 , Hui-Qiong Wang1,3 , Yuan Ping Feng2,† , Jin-Cheng Zheng1,3,4,‡
1
Department of Physics, and Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices,
Xiamen University, Xiamen 361005, China
2
Department of Physics, National University of Singapore, Singapore 117542, Singapore
3
Institute of Artificial Intelligence, Xiamen University Malaysia, 439000 Sepang, Selangor, Malaysia
4
Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen University, Xiamen 361005, China
Corresponding authors. E-mail: † [email protected], ‡ [email protected]
Received December 31, 2018; accepted February 3, 2019

Since two-dimensional boron sheet (borophene) synthesized on Ag substrates in 2015, research on

borophene has grown fast in the fields of condensed matter physics, chemistry, material science, and
nanotechnology. Due to the unique physical and chemical properties, borophene has various poten-
tial applications. In this review, we summarize the progress on borophene with a particular emphasis
on the recent advances. First, we introduce the phases of borophene by experimental synthesis and
theoretical predictions. Then, the physical and chemical properties, such as mechanical, thermal, elec-
tronic, optical and superconducting properties are summarized. We also discuss in detail the utilization
of the borophene for wide ranges of potential application among the alkali metal ion batteries, Li-S
batteries, hydrogen storage, supercapacitor, sensor and catalytic in hydrogen evolution, oxygen reduc-
tion, oxygen evolution, and CO2 electroreduction reaction. Finally, the challenges and outlooks in this
promising field are featured on the basis of its current development.
Keywords borophene, structural diversity, high anisotropy, boron vacancy concentration

Contents materials, such as graphene, BN [12], silicene [13–15], ger-

1 Introduction 1 manene [16], phosphorene [17], transition metal dichalco-
2 Experimental synthesis and theoretical genides [18–23], arsenene [24], and antimonene [24, 25]
prediction 2 have attracted dramatically increasing interest in the past
3 Physical and chemical properties 4 decade. Plenty of 2D materials have been synthesized or
3.1 Mechanical properties 4 theoretically predicted. Due to the unique physical and
3.2 Thermal conductivity 7 chemical properties (such as linear band structure near
3.3 Electronic and optical properties 7 the Fermi level, high electrical, thermal conductance and
3.4 Superconducting properties 8 its stiffness), 2D materials show vast application prospect
4 Application of borophene as energy materials 9 in electronic devices, energy storage and utilization.
4.1 Alkali metal ion batteries 9 Borophene, a single layer of boron atom, has been syn-
4.2 Li-S batteries 10 thesized recently on a silver substrate under ultrahigh-
4.3 Hydrogen storage 11 vacuum [26–28]. All four phases (2-Pmmn, β12 , χ3 and
4.4 Supercapacitor 11 honeycomb phases as shown in Fig. 1) of borophenes that
4.5 Catalytic performances in hydrogen have been synthesized in the experiments are metallic.
evolution, oxygen reduction, oxygen Since then, numerous experimental and theoretical stud-
evolution reaction, and CO2 ies of the mechanical properties, electronic structure, lat-
electroreduction reaction 12 tice thermal conductivity, superconducting properties, op-
4.6 Sensor 13 tical properties, atomic adsorption, and surface reactiv-
5 Summary and prospect 14 ity of borophene have been reported [29–50]. Borophene
Acknowledgements 14 shows some unique physical and chemical properties. For
References 14 instance, the 2-Pmmn phase of borophene possesses a
buckled structure with the adjacent row boron atoms cor-
rugating along the zigzag direction. Along the other in-
1 Introduction plane direction (armchair direction), the atomic structure
is un-corrugated. Interestingly, the Poisson’s ratios along
With the boom of graphene [1–11], two-dimensional (2D) both in-plane directions are negative. Highly anisotropic
mechanical properties have been observed. The Young’s
*arXiv: 1903.11304.

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
 Review article

modulus along the armchair direction can be up to 398 utilization, such as the metal ion batteries, hydrogen stor-
N/m, which is even larger than that of graphene. How- age, sensor and catalytic in hydrogen evolution, oxygen
ever, the Young’s modulus along the zigzag direction is reduction, oxygen evolution, and CO2 electroreduction re-
only 170 N/m [26]. Due to the highly anisotropic crystal actions.
structure, the electronic band structure also shows high
anisotropy. Along the armchair direction, the band struc-
ture shows metallic character; however, along the zigzag 2 Experimental synthesis and theoretical
direction, a large band gap is observed. Ultrafast surface prediction
ion transport along the armchair direction has been found.
The energy barrier of Li/Na/K/Mg/Al ion transport on Due to the large energy difference between borophene
the 2-Pmmn phase of borophene is about 1.9–39.24 meV. and bulk boron, borophene is difficult to be synthe-
Besides, high capacity and excellent electronic conduc- sized. The energy difference between 2-Pmmn phase of
tivity are confirmed. Combined with the high capacity, borophene and the bulk α-rhombohedral boron is about
outstanding electronic and ionic conductivity, borophene 555 meV/atom [51]. To the best of our knowledge, four
shows vast application prospect in metal ion batteries as phases (2-Pmmn, β12 , χ3 and graphene-like phases) of
an anode material. Furthermore, it has been reported that borophene have been synthesized on Ag or Al(111) sub-
borophene can be a catalyst in hydrogen evolution, oxy- strates under ultrahigh-vacuum conditions [26–28]. Be-
gen reduction, oxygen evolution and CO2 electroreduction fore the experimental synthesis, all the four structures
reactions with high catalytic performance. The hydrogen have been predicted by theoretical calculations, showing
molecule adsorption on the metal-decorated borophene the power of theoretical calculations. The scanning tun-
has been studied. The results show that the hydrogen stor- neling microscope (STM) topography images and struc-
age capacity is impressive due to the light mass of the ture models are shown in Fig. 1. For the 2-Pmmn phase
boron element and metal atom decoration. of borophene, highly anisotropic electronic and mechan-
In this review, we first introduce the experimental ical properties have been reported. 2-Pmmn phase of
synthesis and theoretical prediction of borophene. Then, borophene is a corrugated configuration with a buckling
we focus on the physical and chemical properties of height of 0.91 Å. Two borophenes, β12 and χ3 , have been
borophenes, mainly including the mechanical, thermal, synthesized on Ag(111) substrate. These two borophenes
electronic, optical and superconducting properties. Fi- are planar without vertical undulations; however, dif-
nally, we summarize the application in energy storage and ferent periodic boron vacancy distribution patterns have

Fig. 1 STM topography images (a–d), top view (e–h) and side view (i–l) structure models of 2-Pmmn, β12 , χ3 and
graphene-like borophene on Ag/Al(111) substrate. Reproduced from Refs. [26–28].

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Review article

been observed by experiments and first principles calcu- Besides the boron vacancy concentration, the metal
lations. Recently, a graphene-like honeycomb borophene substrate mediation plays a key role in the stability of
has been synthesized on Al(111) substrate. It is very in- borophenes. Yakobson et al. proposed that the ground
teresting that graphene-like borophene is more energeti- state structure of borophene in freestanding state and on
cally stable on Al(111) surface than that on Ag(111) sur- a substrate is not invariable. As shown in Fig. 3, on the
face. Compared with graphene, each boron atom is one Ag(111) surface, β12 phase of borophene (x = 1/6) is
electron deficient. The charge transfer from the Al(111) most stable. The second and third stable structures ap-
substrate to graphene-like borophene is nearly one elec- pear at x = 1/8 and 1/12. The corresponding energy dif-
tron. However, the charge transfer from the Ag(111) sub- ference with respect to the ground state (β12 -borophene)
strate to the graphene-like borophene is negligible. Hence, of the second and third stable structures are only 0.4
for graphene-like borophene, it is more energetically sta- and 2.1 meV [62], respectively, indicating that borophenes
ble on Al(111) surface that on Ag(111) surface. Success- on Ag(111) surface remain polymorphic. However, on the
ful experimental synthesis of the four borophenes boosts Cu(111) surface, all three sheets with the lowest formation
the corresponding fundamental research and enlightens its energy Ef appear at x = 1/6. The corresponding energy
practical application in nanodevices and energy field. differences with respect to the ground state of the sec-
Plenty of 2D boron allotropes have been reported by ond and third stable structures are 15.1 and 28.9 meV
theoretical calculations [44, 52–60]. The results show that [62], respectively, which are much larger than that on
the stability of borophene is closely related to the hexagon Ag(111) surface. This finding shows that it is more likely
boron vacancy concentration x, substrate mediation ef- to form specific borophene structure on Cu(111) surface.
fect, and chemical modification. First, we discuss the ef- In other words, the degree of structural polymorphism of
fect of the hexagon boron vacancy concentration x. Boron borophene decreased.
vacancy concentration is defined as the ratio between the In addition to the boron vacancy concentration and
number of the hexagon boron vacancies and the number of the effect of metal substrate, functionalization is an ef-
atoms in the original triangular sheet. As shown in Fig. 2, fective approach to tune the physical and chemical prop-
the formation energy Ef curve is a V-like function of boron erties of 2D materials. For example, hydrogenation can
vacancy concentration x, which agrees well with other re- open the band gap of graphene, silicene, and germanene.
sults [61]. At x = 1/9, the corresponding structure is the More specifically, before the hydrogenation, graphene, sil-
most stable one. Intriguingly, the formation energy at two icene, and germanene are zero gap semiconductors. How-
slightly higher vacancy concentration, x = 1/8 and 2/15, ever, after the hydrogenation, the band gaps of chair-like
is very close to that at x = 1/9. A considerable number configuration fully hydrogenated graphene, silicene and
of boron allotropes are found whose formation energies germanene are 4.6, 4.0 and 3.6 eV, respectively [63–65].
are within a few meV/atom of the ground-state line. This On the other hand, hydrogenation also has a strong ef-
polymorphism of 2D boron is completely different from fect on the crystal structure of graphene. Graphene is a
other 2D materials: 2D carbon (graphene), Si (silicene), planar structure. Fully hydrogenated graphene is a corru-
Ge (germanene), boron nitride (h-BN) and black phos- gated structure. Hydrogenation can improve the stability
phorus (phosphorene). Graphene, h-BN, silicene, and ger- of 2D materials. 2-Pmmn phase of borophene is not dy-
manene display a distinct honeycomb structure. namically stable due to the imaginary frequency around
the Γ point in the Brillouin zone. After hydrogenation, the
imaginary frequency is removed, indicating that hydro-
genation can improve the dynamic stability of borophene
[66–68]. The electronic band structure also changes due to
the hydrogenation. 2-Pmmn shows a metallic band struc-
ture with some electrons occupy the antibonding states.
During the hydrogenation process, a 0.75e charge transfer
from boron to hydrogen atoms has been confirmed [67],
leading to the results that the in-plane bonding states
are completely occupied, antibonding states are empty
and the out-plane bonding states are also fully occupied.
Finally, fully hydrogenated 2-Pmmn phase of borophene
possesses a Dirac cone along the X-Γ direction in the Bril-
louin zone with the Dirac point located at the Fermi level
perfectly. Ultrahigh Fermi velocity of 3.5 × 106 m/s [67],
which is even larger than that of graphene, has been ob-
served. The Young’s modulus of the fully hydrogenated
Fig. 2 Formation energies Ef of borophenes as a function 2-Pmmn phase of borophene along the two in-plane direc-
of boron vacancy concentration x. Reproduced from Ref. [52]. tions are 172.24 and 110.59 N/m, respectively [68]. The

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 Review article

Fig. 3 Configurational energy spectra of freestanding and Au, Ag, Cu, and Ni substrates supported borophenes. Reproduced
from Ref. [62].

ultimate tensile strains along the zigzag and biaxial di- Young’s modulus along the armchair direction is 398 N/m
rections can be up to 0.30 and 0.25, respectively [68]. [34], also larger than that of graphene. The Young’s mod-
Fermi velocities can be tuned in a large range by mechani- ulus along the zigzag direction (170 N/m) is much smaller.
cal strains. Three other hydrogenated borophenes (C2/m, Due to the corrugated structure, the in-plane Poisson’s ra-
Pbcm, and Cmmm phase of borophane) are proposed by tios (−0.04 along the armchair direction and −0.02 along
Jiao et al. The related atomic structure, electron local- the zigzag direction) are negative. The critical strains of
ization function (ELF) and band structure are shown in borophene and other related 2D materials are listed in Ta-
Fig. 4 and Fig. 5. The dynamic stability of the three hy- ble 2. The ultimate strains of 2-Pmmn phase of borophene
drogenated borophenes has been confirmed by phonon dis- along the zigzag and armchair directions are 0.15 and
persions calculations. No imaginary modes can be found in 0.10, respectively. The corresponding stresses are 12.95
the phonon dispersions. The C2/m and Pbcm phase of hy- and 27.46 N/m, respectively [73]. When the strain along
drogenated borophenes possess Dirac cones with massless the zigzag direction is 0.1, the corresponding stress is only
Dirac fermions and the Fermi velocities for the Pbcm and about 11.1 N/m, which is much lower than that under the
Cmmm structures are even higher than that of graphene same strain value along the armchair direction. Due to the
[66]. More intriguingly, the Cmmm borophane shows a compensation of the dihedral angle and B-B bond angles
Dirac ring [as shown in Fig. 5(f)], which is the first report along the zigzag direction, it is easier to apply strain along
among the boron-based 2D materials. the zigzag direction. Along the biaxial direction, the ulti-
mate strain is 0.13, and the corresponding stress is about
23 N/m.
3 Physical and chemical properties The mechanical properties of borophene are affected by
the borophene vacancy defect, chemical modification, the
3.1 Mechanical properties number of layers and temperature. Each of these aspects
is discussed in the following.
Tremendous interest is focused on the mechanical proper- First, the effects of the boron vacancy defect on the me-
ties of borophenes [45, 53, 69–72]. Due to the strong B-B chanical properties were first reported by Mortazavi et al.
bonds and unique atomic structure, ultrahigh mechani- [70]. Their results show that the Young’s modulus along
cal modulus of borophene has been reported. The elastic the armchair direction decreases almost linearly with in-
constants cij , layer modulus γ, shear modulus G, Young’s creasing defect concentration. For β12 and χ3 , the Young’s
modulus Y in N/m, and Poisson’s ratio ν of borophene, modulus along the armchair direction is 179.00 and 198.50
borophane and common 2D materials are listed in Table N/m, respectively, which are much smaller than that of
1. The Young’s modulus of Pmmm phase of borophene the perfect 2-Pmmn phase of borophene (398 N/m). How-
along the armchair direction can be up to 574.61 N/m, ever, along the zigzag direction, the effect of boron va-
which is much larger than that of graphene (338.08 N/m) cancy concentration on the Young’s modulus is relatively
[68]. 2-Pmmn phase of borophene shows highly anisotropic small. Interestingly, in contrast to the negative Poisson’s
mechanical properties and negative Poisson’s ratio. The ratio of the defect-free 2-Pmmn phase of borophene, the

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Fig. 4 (a–f) Top and side view atomic structure, (g–i) 2D ELF figure along (001) direction, (j–l) 3D ELF (isovalue = 0.75)
of C2/m, P bcm, and Cmmm borophanes. Reproduced from Ref. [66].

Fig. 5 (a–c) Band structures and density of states and (d–f) the 3D band plots for C2/m, P bcm, and Cmmm borophanes.
Reproduced from Ref. [66].

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Table 1 Elastic constants cij , layer modulus γ, shear modulus G, Young’s modulus Y in N/m, and Poisson’s ratio ν of
borophene, borophane and common 2D materials, respectively.

c11 c22 c12 c66 = G Ya Yb νa νb

ML 2-Pmmn [68] 379.00 162.50 −2.00 87.00 378.97 162.49 −0.012 −0.005
[34] 398.00 170.00 −7.00 94.00 398.00 170.00 −0.040 −0.020
[78] 396.60 158.40 −3.47 86.50 397 158 −0.022 −0.009
BL 2-Pmmn [78] 380.0 143.8 7.44 75.2 380 144 0.052 0.020
2-Pmmn 3Layer [78] 361.1 141.5 11.29 73.5 360 141 0.080 0.031
2-Pmmn 4Layer [78] 337.9 136.0 12.37 70.8 338 136 0.091 0.037
B4 F [74] 275.06 183.66 13.07 79.63 274.13 183.04 0.07 0.05
B2 F [74] 130.12 200.76 6.17 57.35 129.93 200.46 0.03 0.05
α sheet [68] 219.00 219.00 43.00 88.00 210.56 210.56 0.196 0.196
β12 [68] 185.50 210.50 37.00 68.50 179.00 203.12 0.176 0.199
χ3 [68] 201.00 185.00 21.50 60.50 198.50 182.70 0.116 0.107
Pmmm [68] 333.50 576.00 21.50 157.00 332.70 574.61 0.037 0.064
8-pmmn [68] 249.00 322.50 15.50 108.00 248.26 321.54 0.048 0.062
BNRN χ-h1 [79] 138.25 138.25 39.25 50.50 127.12 127.12 0.284 0.284
C-borophane [68] 175.77 112.86 19.97 28.46 172.24 110.59 0.177 0.144
B-borophane [80] 197.00 83.00 22.00 53.50 191.17 80.54 0.265 0.112
TCB-borophane [80] 160.00 122.00 29.00 70.00 153.11 116.74 0.238 0.181
T-borophane [80] 129.50 154.00 27.50 79.50 124.59 148.16 0.179 0.212
W-borophane [80] 179.50 159.00 21.00 84.00 176.73 156.54 0.132 0.117
Graphene [68] 348.75 348.75 61.00 143.88 338.08 338.08 0.175 0.175
Ref. [81] 352.70 352.70 60.90 145.90 342.18 342.18 0.173 0.173
Ref. [82] 358.10 358.10 60.40 148.90 347.91 347.91 0.169 0.169
BN [81] 289.8 289.8 63.7 113.1 275.8 275.8 0.22 0.22
Phosphorene [79] 186.80 44.61 31.23 41.82 167.88 39.39 0.70 0.167
Silicene [81] 68.3 68.3 23.3 22.5 60.6 60.6 0.341 0.341
Germanene [81] 46.4 46.1 13.1 16.7 42.7 42.7 0.282 0.282

Table 2 The critical strain of borophenes and common 2D borophene to its corrugated structure. However, all the
materials. For 8-Pmmn phase of borophene, we define the di- critical strains for α sheet, β12 and χ3 along the two in-
rection along the atomic wrinkle direction as the zigzag di- plane directions are larger than that of the defect-free 2-
rection and the corresponding perpendicular direction as the Pmmn phase of borophene.
armchair direction. Chemical modification has a strong effect on the me-
chanical properties of borophene. The Young’s modulus of
Armchair/ Zigzag/
a-direction b-direction Biaxial the fully hydrogenated 2-Pmmn phase of borophene along
the two in-plane directions are 172.24 and 110.59 N/m,
ML 2-Pmmn [83] 0.08 0.15 0.08
Ref. [73] 0.10 0.15 0.13
respectively [68]. The dramatical decrease can be under-
BL 2-Pmmn [78] 0.14 0.16 0.13 stood from the atomic structures. Before hydrogenation,
2-Pmmn 3Layer [78] 0.14 0.16 0.15 the B–B bond length along the armchair direction is 1.616
2-Pmmn 4Layer [78] 0.14 0.15 0.14 Å, which is stretched to 1.941 Å up on hydrogenation.
β12 [83] 0.20 0.12 This bond elongation leads to the decrease in the bond
Ref. [73] 0.21 0.18 0.16 strength, and a reduction in the Young’s modulus. On
χ3 [83] 0.11 0.21 the other hand, hydrogenation increases the critical strain.
8-Pmmn [83] 0.16 0.17 0.13 The critical strains of 2-Pmmn phase of borophene along
BNRN χ-h1 [79] 0.51 0.41 0.84
the a-, b- and biaxial directions are 0.08, 0.15 and 0.08,
Graphene [84] 0.19 0.24 0.24
respectively. After the hydrogenation, the critical strains
BN [84] 0.18 0.26 0.24
MoS2 [83] 0.26 0.18 0.22
increase to 0.12, 0.30 and 0.25, respectively [68]. Fluori-
Phosphorene [83] 0.27 0.33 nation has a similar effect on the mechanical modulus of
Silicene [83] 0.17 0.14 0.16 2-Pmmn phase of borophene. For B4 F, the Young’s modu-
Germanene [85] 0.20 0.21 lus along the two in-plane directions are 274.13 and 183.04
Stanene [85] 0.17 0.18 N/m, respectively. For B2 F, the corresponding values are
129.93 and 200.46 N/m, respectively [74], showing a dra-
Poisson’s ratios of the α sheet, β12 and χ3 phases are matic decrease of the Young’s modulus along the armchair
positive. By analyzing the crystal structure, we can at- direction.
tribute the negative Poisson’s ratio of 2-Pmmn phase of The number of layers in multi-layer 2-Pmmn phase of

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borophene also has a strong effect on its mechanical prop- phonon transmission of hydrogenated 2-Pmmn phase of
erties. From one layer to four layers, the Young’s modulus borophene has been proposed by Li et al. [86], i.e., the
of 2-Pmmn phase of borophene along the armchair direc- phonon transmission of low-frequency phonons shows 2D
tion is 397, 380, 360 and 338 N/m, respectively. Along behavior, however, at high-frequency, the phonon trans-
the zigzag direction, the corresponding Young’s modulus mission shows 1D behavior. The transmission of high-
is 158, 144, 141 and 136 N/m, respectively. The Young’s frequency phonons is close to 0 nm−1 . Due to the excel-
moduli along the two in-plane directions decrease with in- lent mechanical properties and high thermal conductiv-
creasing number of layers. A similar phenomenon has been ity, hydrogenated 2-Pmmn phase of borophene is promis-
observed in black phosphorene [75]. ing for the soft thermal channel. The unique dimension-
The Young’s modulus of borophene was found to de- ality crossover in phonon transmission provides a good
crease with temperature [72, 76]. For borophene with a approach to study the effect of phonon population, which
boron concentration x of 4/27, the Young’s modulus along is important for thermal transport in low-dimensional sys-
the zigzag direction is 180 N/m at 1 K, which is reduced tems.
to 87 N/m at 600 K.
Due to the structural polymorphism of borophene,
3.3 Electronic and optical properties
unique mechanical properties (negative Poisson’s ratio,
ultrahigh Young’s modulus, high anisotropy) have been The electronic structure of 2-Pmmn phase of borophene
found. Furthermore, in our previous work, extraordinary is also highly anisotropic [80]. More specifically, the elec-
mechanical properties have been found in boron nanorib- tronic band structure shows metallic conduction along the
bon networks. Due to the breaking of the B–B bonds and Γ-X and Y-S directions (armchair direction). A high group
the rotation of the local structures, structural phase tran- velocity of 6.6 × 105 m/s has been confirmed [51]. How-
sition occurs under the a-, b-direction uniaxial and biax- ever, the band structure shows a band gap along the Γ-Y
ial strains. Subsequently, successive phase transition gen- and S-X directions (zigzag direction).
erates ultrahigh critical tensile strains. The critical ten- Chemical modification is an effective approach to tune
sile strains of χ-h1 boron nanoribbon network along the the band structure of 2D materials. Band gap opening has
a- and b-direction are 0.51 and 0.41, respectively. Along been found in graphene, silicene, and germanene by hydro-
the biaxial direction, the critical strain is 0.84, which is genation and fluorination. The band structure of 2-Pmmn
ultrahigh compared to other 2D materials. Furthermore, phase of borophene is metallic. However, for the fully hy-
the structural phase transition can effectively decrease the drogenated 2-Pmmn phase of borophene, the band struc-
strain energy, making the boron nanoribbon network eas- ture change to a zero-gap semiconductor. A Dirac cone has
ier to stretch. Surprisingly, outstanding electronic trans- been found and the Dirac point is perfectly located at the
port properties of χ-h1 boron nanoribbon network has Fermi level. The transition from metallic band structure to
been verified by Yi el al. [77] The outstanding flexibil- zero gap semiconductor band structure has been reported.
ity and excellent electronic conductivity lead to a vast Moreover, the effect of fluorination on the band structure
promising application of borophene in flexible electronic of 2-Pmmn phase of borophene has been studied by first
devices. principles calculations. Two stable fluorinated borophene
structures, B4 F and B2 F, were proposed. For B4 F, the
3.2 Thermal conductivity metallic electronic band structure is preserved. However,
B2 F is an indirect semiconductor with a band gap of 0.4
Thermal conductivity is an important physical param- eV [74]. The thermodynamic stability of B4 F and B2 F at
eter for the performance and longevity of nano de- finite temperatures has been evaluated by using first prin-
vices. The thermal conductivity and phonon transmis- ciples molecular dynamics (FPMD) simulation. The re-
sion of borophene have been studied [86–92]. Due to the sults show that both B4 F and B2 F are stable even at 1000
highly anisotropic atomic structure of 2-Pmmn phase of K. The intrinsic semiconducting electronic band structure,
borophene, the thermal conductivity is anisotropic. At the excellent mechanical properties, and the good stability
room temperature, the thermal conductivity of 2-Pmmn make the fluorinated borophene a promising candidate in
phase of borophene is ∼ 75.9 and ∼ 147 W/mK along semiconductor electronic devices.
the zigzag and armchair directions, respectively. The ef- Generally speaking, mechanical strain can have a strong
fective phonon mean free path is 16.7 and 21.4 nm along effect on the physical and chemical properties of materi-
the two directions, respectively. For α-sheet borophene, als [95–98]. The effects of external mechanical strains on
an isotropic material, the thermal conductivity is 14.34 the electronic band structure of the Pbcm phase of boro-
W/mK. Surprisingly, the thermal transport is dominat- phane have been investigated. The results show that uni-
ingly contributed by high-frequency phonon modes. For axial strains along either in-plane direction does not open
graphene [93], silicene [93] and phosphorene [94], the ther- a gap at the Dirac point. However, a band gap can be open
mal transport is dominated by the low-frequency acous- at the Dirac point by a shear strain. At a shear strain of
tic modes. In addition, a dimensionality cross-over of the 0.01, the strain-induced band gap was found to be 55 meV

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[99]. Furthermore, the shear strain induced band gap in- borophene materials. For the absorption and reflectivity
creases with the increasing shear strain. At a share strain coefficient, the positions of the main absorption are dif-
of 0.12, the band gap reaches 538 meV [99]. The excellent ferent along the two in-plane directions. Along the arm-
dynamical stability of Pbcm borophane under the shear chair direction, the absorption regions are around 3.65
stain has been confirmed by the phonon dispersion. Shear and 10.36 eV. However, the main absorption peaks are
strain induced band gap opening was also found in fully located at around 1.09, 8.29 and 10.31 eV, respectively
hydrogenated 2-Pmmn phase of borophene. Similarly, the [100]. Furthermore, in the visible region, the reflectivity
band gap increases with the increasing shear strain. A of borophene along the armchair and zigzag directions are
similar effect of mechanical strain on the band structure <30% and >40%, respectively. Both the transmittance
of 8-Pmmn phase of borophene has been reported. Here, and electrical conductivity of 2-Pmmn phase of borophene
neither uniaxial nor biaxial strain cannot open a gap at the along the armchair direction is higher than that along
Dirac point. However, gap opening at the Dirac point can the zigzag direction. The optical conductivity of 2-Pmmn
be achieved by a shear strain. Unexpectedly, under the phase of borophene is very small in the visible region. How-
stress-free state, hydrogenated graphene-like borophene ever, fluorinated 2-Pmmn phase of borophene (B2 F) shows
possesses a metallic band structure. A metallic to semi- significant optical conductivity in the visible region, sug-
conducting band structure transition can be induced by gesting promising applications in optical devices.
a uniaxial and a biaxial strain. More specifically, under
a b-direction uniaxial or biaxial strain of 0.2, the band 3.4 Superconducting properties
gap is 380 and 120 meV, respectively. The unique effect of
mechanical strains on the band structure of hydrogenated Superconductivity properties of borophene have been re-
graphene-like borophene has been observed. The strain- ported in various studies [29, 54, 61, 101–106]. Zhao et
induced band structure transition provides a new enlight- al. carried out a systematic study of borophene with a
enment for us to tune the band structure of 2D materials. range of boron vacancy concentration [61]. As shown in
Anisotropic optical properties have been found in Fig. 6, it is very intriguing that the superconducting tran-

Fig. 6 (a) Most stable borophenes under different boron vacancy concentration η (η = x in this paper). (b) Total energy and
NF vs. boron vacancy concentration. The total energy of α sheet is set to be zero. (c) λ and Tc vs. boron vacancy concentration.
Reproduced from Ref. [61].

33403-8 Zhi-Qiang Wang, et al., Front. Phys. 14(3), 33403 (2019)

Review article

sition temperature Tc shows a V-shaped dependence on creasing in-plane projected density of states at the Fermi
the hexagon hole density. The superconducting transition level, rather than with total density of states. This finding
temperature Tc was found to decrease gradually with in- provides an effective approach to tune the superconductiv-
creasing boron vacancy concentration, up to x = 1/9, be- ity of free-standing, substrate-supported borophene and
yond which Tc increases gradually with the boron vacancy metal intercalated bilayer borophenes. Besides the above
concentration. In addition to the superconducting transi- two avenues (strain and carrier doping) that can tune
tion temperature Tc , V-shaped dependence on boron va- Tc , the superconductivity properties of borophene are also
cancy concentration was also found for total energy, elec- closely related to its intrinsic crystal structure. Borophene
tronic density of states NF at the Fermi level, electron- shows a certain application prospect in superconductivity
phonon coupling (EPC) parameter λ. The inflection points with a high superconducting transition temperature.
of the above four curves are located at the x = 1/9. This
work provides a useful approach to analyze the stability
and superconducting properties of 2D materials. A posi- 4 Application of borophene as energy
tive correlation between the density of state at the Fermi materials
level and the superconducting property has been observed
in borophene and transition metal intercalated bilayer 4.1 Alkali metal ion batteries
borophene.
For 2-Pmmn phase of borophene, high density of states For electrode materials, high capacity, suitable voltage,
at the Fermi energy and strong Fermi surface nesting lead good electronic and ionic conductivity are crucial param-
to strong electron-phonon coupling. The superconducting eters. Borophene is the lightest 2D material. Furthermore,
transition temperature Tc of freestanding 2-Pmmn phase high surface activity of borophene has been reported.
of borophene is about 19 K. Furthermore, Tc can be tuned Both of these two factors are beneficial to achieve ultra-
by strain and carrier doping. More specifically, a tensile high capacity for Li/Na/K/Mg/Al storage. The metallic
strain can increase Tc to 27.4 K, while hole doping can in- band structure is also good for electronic conductivity.
crease Tc to 34.8 K [35]. On the other hand, a compressive Hence, borophene can be a promising electrode material
strain or electron doping decreases Tc of 2-Pmmn phase for Li/Na/K/Mg/Al ion batteries.
of borophene. The electron-doping induced suppression of Zhao et al. firstly proposed 2-Pmmn borophane as a
the superconductivity properties was also found in the β12 good anode materials for Li ion batteries. Due to the high
phase of borophene. The superconducting transition tem- surface activity of 2-Pmmn phase of borophene, the in-
perature of β12 phase of borophene is 14 K. Electron dop- teraction between Li and borophene is strong. The ini-
ing of 0.1e per boron atom reduces Tc to 0.09 K. The im- tial intercalation voltage (at low Li adsorption coverage)
pact of strain and carrier doping on Tc is closely related is 1.12 eV, and decreases with increasing Li adsorption
to the density states of in-plane orbitals near the Fermi coverage. The fully lithiated phase of 2-Pmmn phase of
surface. The electron-doping induced suppression explains borophene is Li0.75 B which corresponds to a theoretical
the challenges to experimentally probe superconductivity specific capacity of 1860 mAh/g, much larger than that of
in substrate-supported borophene. graphite (372 mAh/g) [107], silicene (954 mAh/g) [108],
In addition, the superconductivity properties of Mg in- phosphorene (433 mAh/g) [109], VS2 (466 mAh/g) [110],
tercalated bilayer borophene systems Bx MgBx (x = 2– Ti3 C2 (320 mAh/g) [111] and Li4 Ti5 O12 (175 mAh/g)
5) have been studied by first principle calculations. Both [112]. Furthermore, as shown in Fig. 7, the Li ion migra-
B2 MgB2 and B4 MgB4 exhibit good phonon-mediated su- tion barrier along the armchair direction is only 2.6 meV,
perconductivity with a high Tc of 23.2 and 13.3 K, respec- indicating ultrafast Li ion migration along the armchair
tively [101]. In the Mg-B systems, Tc decreases with de- direction. The Li ion migration barrier of 2-Pmmn phase

Fig. 7 (a) Energy barri-

ers, and (b), (c) pathways
of Li migration along zigzag
and armchair directions. Re-
produced from Ref. [107].

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 Review article

of borophene is much smaller than that of graphite (450– mAh/g, respectively, which are much higher than those of
1200 meV) [107], silicene (230 mAh/g) [108], phospho- graphene, silicene, phosphorene, and Li4 Ti5 O12 . However,
rene (80 mAh/g) [109], and Li4 Ti5 O12 (300 mAh/g) [112]. due to the periodically arranged boron vacancies and the
However, along the zigzag direction, the energy barrier of structural transition from the corrugated structure to the
2-Pmmn phase of borophene is about 325 meV. Hence, the flat structure, the migration energy barriers of Li, Na and
surface Li ion migration shows strong anisotropy. During Mg on β12 and χ3 phases of borophene are larger than that
the whole lithiation process, the electronic structures are on 2-Pmmn phase of borophene. But the energy barrier
metallic characteristic, indicating excellent electronic con- is still acceptable as anode materials for Li/Na ion bat-
ductivity of borophene. The ultrahigh ionic conductivity teries. As listed in Table 3, the migration energy barrier
and excellent electronic conductivity guarantee an out- of Na ion (330 meV) for β12 phase of borophene is much
standing rate performance of 2-Pmmn borophene during smaller than that of Li ion (660 meV). Similarly, for χ3
the charging and discharging process. phase of borophene, the migration energy barrier of Na ion
Applications of 2-Pmmn phase of borophene in Na, K, (340 meV) is much smaller than that of Li ion (600 meV).
Mg, Ca, Al ion batteries have also been reported. Ultra- Therefore, from the point of view of ionic conductivity and
high capacity and ultrafast ion diffusion of 2-Pmmn phase rate performance, borophene with boron vacancies can be
of borophene have been identified. More specifically, the expected to perform better as an anode material in Na ion
capacities of 2-Pmmn phase of borophene as an anode batteries than in Li ion batteries.
material are 6611 and 9917 mAh/g for Mg and Al ion Thus, borophene is a promising anode material for Li,
batteries, respectively. The energy barriers of Mg and Al Na and Mg ion batteries due to high theoretical specific
ion migration along the armchair direction are only 11.76 capacities, excellent electronic conductivity and outstand-
and 39.24 meV, respectively. ing ion transport properties [107, 115–121].
Furthermore, doping is a common approach to tune the
physical and chemical properties of functional materials 4.2 Li-S batteries
[113, 114]. The effects of P doping, hydrogenation and
substrate have been studied. Hydrogenation can stabi- The advance of lithium-sulfur batteries has been ham-
lize 2-Pmmn phase of borophene by the charge transfer pered by the fast capacity fading induced by the shuttle
from borophene to hydrogen atoms. Hence, the interac- effect [127]. Suitable sulfur anchoring materials can sup-
tions strength between Li and hydrogenated borophene press the shuttle effect and improve the cycling perfor-
decreases. As an anode material for Li ion batteries, the mance. The interaction between the anchoring material
capacity of hydrogenated 2-Pmmn phase of borophene is and lithium polysulfides should not be too strong or too
504 mAh/g, which is much lower than that of 2-Pmmn weak. As listed in Table 4, for graphene, the adsorption
phase of borophene (1860 mAh/g). energies of Li2 S4 , Li2 S6 , and Li2 S8 are 0.65, 0.72 and 0.73
In addition, the β12 and χ3 phases of borophene also eV, respectively. Due to the weak interaction, graphene is
show high capacities in Li, Na, and Mg ion batteries. As not a suitable anchoring material for lithium polysulfides.
the anode material, the capacities of β12 and χ3 phases It is imperative to search for more suitable anchoring ma-
of borophene in Li ion batteries reach 1984 and 1240 terials for lithium batteries.

Table 3 The theoretical specific capacity (C) and diffusion barriers (Ea ) of borophene and some common 2D materials as
anode materials for alkali metal ion batteries.

Species M C (mAh/g) Ea (meV) Ref. Species M C (mAh/g) Ea (meV) Ref.

2-Pmmn Li 1860 2.6 [107] β12 Li 1880 690 [122]
Li 3306 10.53 [119] Na 1984 330 [116]
Li 1239 7 [123] Na 1640 340 [122]
Na 1218 1.9 [117] Mg 2480 970 [122]
Na 2341 2.55 [119] χ3 Li 1240 600 [116]
K 1377 7.61 [119] Li 1240 475 [124]
Mg 6611 11.76 [119] Li 2040 [122]
Al 9917 39.24 [119] Na 1240 340 [116]
2-Pmmn/Ag Li 33 [123] Na 1480 [122]
2-Pmmn-P Li 1732 328 [125] Mg 2400 [122]
2-Pmmn-H Li 504 210 [126] Graphite Li 372 450-1200 [107]
2-Pmmn-H Na 504 90 [126] Phosphorene Li 433 80 [109]
β12 Li 1984 660 [116] Silicene Li 954 230 [108]
Li 1983 590 [124] Li4 Ti5 O12 Li 175 300 [112]

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Review article

Table 4 The adsorption energies (in eV) of Li2 S, Li2 S2 , Table 5 The adsorption energies Eb and hydrogen storage
Li2 S4 , Li2 S6 and Li2 S8 on 2-Pmmn, χ3 , β12 borophene, capacity of the metal atom (M) decorated borophenes, defec-
graphene, and phosphorene. tive 2-Pmmn borophene, graphene, graphyne, silicene, BC7 ,
MoS2 , and AlN. The η value in the bracket is the boron va-
Species Li2 S Li2 S2 Li2 S4 Li2 S6 Li2 S8 Ref. cancy concentration.
2-Pmmn 6.45 4.32 6.18 [131]
Species M Eb (eV) Capacity (wt %) Ref.
χ3 2.67 2.53 2.87 [131]
α-sheet Li 0.15 10.75 [134]
β12 3.34 2.89 1.45 1.53 1.36 [128]
Na 0.07 8.36 [134]
Graphene 0.65 0.72 0.73 [132] K 0.06 2.39 [134]
Phosphorene 2.51 1.91 1.27 1.00 1.12 [133] Ca 0.19 12.68 [138]
Borophene (η = 1/8) Li 0.23 15.26 [144]
Borophene (η = 1/7) Li 0.35 9.22 [143]
The application of borophene as the potential anchor- β12 Li 0.22 10.85 [147]
ing materials for lithium-sulfur batteries has been stud- Ca 0.24 9.5 [137]
ied by first principles calculations [128–130]. Zhao et al. 2-Pmmn Li ∼ 0.11 6.8 [139]
concluded that the 2-Pmmn phase of borophene is not a Na ∼ 0.11 9.0 [139]
good anchoring material for the excessively strong inter- Ca ∼ 0.11 7.6 [139]
action between lithium polysulfides and 2-Pmmn phase 2-Pmmn with double ∼ 0.10 9.2 [139]
of borophene. The adsorption energies of Li2 S4 , Li2 S6, vacancy
and Li2 S8 on 2-Pmmn phase of borophene are 6.45, 4.32 χ3 Ca 0.23 7.2 [137]
χ-h0 Na 0.15 8.28 [148]
and 6.18 eV, respectively. Such strong interactions will
Graphene Li 0.21 12.8 [149]
lead to the decomposition of lithium polysulfides, result-
Graphyne Li 0.19 13.0 [150]
ing in the irreversible sulfur loss during the charging and
Silicene Li 0.26 6.35 [151]
discharging processes. Unexpectedly, the interaction be-
BC7 Ca 0.26 4.96 [152]
tween lithium polysulfides and the χ3 phase of borophene
MoS2 Li 0.20 4.80 [153]
is much smaller than that between the lithium polysul-
AlN 0.13 8.90 [154]
fides and 2-Pmmn phase of borophene, but larger than
that between lithium polysulfides and graphene. The ad-
sorption energies of Li2 S4 , Li2 S6 , and Li2 S8 on χ3 phase
molecule with the α-sheet phase of borophene shows sim-
of borophene are 2.67, 2.53 and 2.87 eV, respectively,
ilarities to its interaction with graphene (0.025 eV) [134].
indicating that χ3 phase of borophene is a suitable an-
The adsorption energy is too small for practical hydrogen
choring material for lithium-sulfur batteries. The suitable
storage. Metal atom decoration is an effective and feasible
adsorption strength is helpful to suppress the shuttle ef-
approach to strengthen the interaction. After Li decora-
fect and keep their cyclic structure undecomposed dur-
tion of α-sheet phase of borophene, the adsorption en-
ing the charging and discharging processes. Furthermore,
ergy of H2 molecule reaches 0.35 eV, a significant increase
borophene shows a metallic electronic structure during the
compared to that without the Li decoration. As shown in
whole battery cycling. Hence, χ3 phase of borophene is a
Fig. 8, up to three H2 molecules can be adsorbed on a Li
promising anchoring material for lithium-sulfur batteries.
atom. This is equivalent to a hydrogen storage capacity of
In addition, the β12 phase of borophene also shows good
10.7 wt %, which is much higher than that of Li-decorated
performance as the anchoring material for Lithium-sulfur
silicene (6.3 wt %) and MoS2 (4.8 wt %). In Table 5, we
batteries. The adsorption energies of Li2 S, Li2 S2 , Li2 S4 ,
list the adsorption energies and hydrogen storage capac-
Li2 S6 , and Li2 S8 on β12 phase of borophene are 3.34, 2.89,
ities of the defective 2-Pmmn phase of borophene, AlN,
1.45, 1.53 and 1.36 eV, respectively. Furthermore, during
metal atom decorated borophenes, graphene, graphyne,
the whole charging and discharging processes, β12 phase
silicene, BC7 , and MoS2 . High hydrogen storage capacity
of borophene shows metallic electronic structure. Thus,
of 10.75 (12.68) wt% for Li (Ca)-decorated α-sheet phase
both the χ3 and β12 phases of borophenes are promising
of borophene and 15.26 wt% for Li-decorated borophene
anchoring materials for lithium-sulfur batteries.
(x = 1/8) have been reported, indicating that alkalis or
alkaline metal decorated borophene shows the application
4.3 Hydrogen storage prospect in hydrogen storage.

As the lightest 2D material, borophene is also a promising 4.4 Supercapacitor

material for hydrogen storage, and can lead to ultrahigh
hydrogen storage capacity. This has been investigated in Few-layer boron sheets exhibit excellent performance
a number of studies [134, 135, 146]. as supercapacitor materials [103]. High-quality few-layer
For the α-sheet of borophene, the adsorption energy of a boron sheets have been synthesized in a large quantity
single H2 molecule is only 0.047 eV. The interaction of H2 by sonication-assisted liquid-phase exfoliation. Due to the

33403-11 Zhi-Qiang Wang, et al., Front. Phys. 14(3), 33403 (2019)

 Review article

Fig. 8 Crystal structures of α sheet borophene without (a) and with (b), (c) Li adsorption. (d, e) Crystal structures of
Li-decorated α sheet borophene with hydrogen molecules adsorption. Reproduced from Ref. [134].

protection of the residual solvent, the exfoliated few-layer lution at a scan rate of 1 mV·s−1 . The electrocatalytic ac-
boron sheets exhibit excellent stability away from the air tivity of carbon sheet is very poor. Amorphous boron and
oxidation. A wide potential window of up to 3.0 V and a Mo are known to have much better performances than
high energy density of 46.1 Wh/Kg have been reported. carbon sheet. The electrocatalytic activities of the four
After 6000 cycles, the capacitance retention of the initial molybdenum borides (Mo2 B, α-MoB, β-MoB and MoB2 )
specific capacitance remains about 88.7%, indicating an are even better than that of amorphous boron and Mo.
impressive cycling stability. This experimental study not The ranking of the electrocatalytic activity is amorphous
only shows us that few layer boron sheets can be synthe- B < Mo < Mo2 B < α-MoB < β-MoB < MoB2 . The
sized in a controlled manner but also broadens the prac- electrocatalytic activity increases with increasing boron
tical application prospect of boron sheets. amount. A boron-dependency of the four borides for the
HER activity has been observed. Similar findings were re-
4.5 Catalytic performances in hydrogen evolution, ported recently in two phosphide systems (HER activity:
oxygen reduction, oxygen evolution reaction, Mo<Mo3 P<MoP) [161]. In addition, the stability mea-
and CO2 electroreduction reaction surements results of β-MoB and MoB2 for the first and the
1000th cycle in 0.5 m H2 SO4 are shown in Fig. 10(c). The
Borophene is the lightest catalyst for hydrogen evolution results show that MoB2 and β-MoB show excellent cat-
reaction (HER) [155, 156]. Wang et al. proposed that alytic performance in HER. The high-performance main-
borophene is a high-performance catalyst for HER with tains well after a long-term cycle.
near zero free energy of hydrogen adsorption, metallic con- As shown in Fig. 11, Jung et al. proposed that boro-
ductivity and plenty of active sites in the basal plane [155]. phane supported single transition metal atoms show high
For 2-Pmmn phase of borophene, due to the high surface catalytic performance in oxygen evolution reaction (OER)
activity, the interaction between H atom and borophene and oxygen reduction reaction (ORR) [162] The increase
is too strong. However, for the χ3 phase of borophene, the of the density of states near the Fermi level induced by
active site is the 5-coordinated boron atoms, and as shown the coupling of the d orbit of TM atoms and surrounding
in Fig. 9, the free energy of hydrogen adsorption ∆GH is B atoms can generate active reactive sites for OER and
only 0.02 eV that is even closer to zero than that on Pt ORR. Among the TM-BH systems, Fe-BH and Rh-BH
(−0.09 eV) [157]. Furthermore, the metallic band struc- are promising ORR electrocatalysts with overpotentials
ture of χ3 phase of borophene and the multiple active of 0.43 V and 0.47 V, respectively, whereas, for the OER,
sites in the basal plane are beneficial to achieve outstand- the overpotential of Rh-BH system is only 0.24 V, which
ing HER catalytic performance. Moreover, for β12 phase is smaller than that of RuO2 (0.37 V) [163]. Borophene
of borophene, the best active site is the 4-coordinated also shows good performance as a CO2 capture material
boron atoms and the corresponding ∆GH is only 0.1 eV. [164, 165]. For the negatively charged β12 borophene, the
A small free energy of hydrogen adsorption ∆GH has also CO2 capture capacity is up to 6.73×1014 cm−2 . Reversible
been found in α-sheet and β1 phase of borophene. Fur- CO2 capture/release processes on the negatively charged
thermore, the high catalytic activity of borophene is not β12 phase of borophene has been observed. The charge and
destroyed by a silver substrate. A similar conclusion has discharge processes can be controlled by switching on/off
been drawn by Sun et al. [158] Borophene shows vast ap- the charges carried by β12 phase of borophene. In addition,
plication prospect in the hydrogen evolution reaction. Sun et al. proposed a constructive strategy to design a new
Moreover, the high catalytic activity of molybdenum catalyst for CO2 electroreduction [166] The results show
boride has been demonstrated experimentally [159, 160] It that the borophene supported Cu chains possess high cat-
is interesting that the crystal structure of MoB2 contains alytic activity for CO2 electroreduction by providing sec-
graphene-like borophene subunits, as shown in Fig. 10(a). ondary adsorption sites, thus leading to small overpoten-
Figure 10(b) shows the electrocatalytic activity of Mo2 B, tials in the preferable reaction pathway CO2 → COOH*
α-MoB, β-MoB and MoB2 measured in a 0.5 M H2 SO4 so- → CO* → CHO* → CH2 O* → CH3 O* → CH3 OH.

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Review article

Fig. 9 Crystal structures of (a) β12 , (b) χ3 , (c) 2-Pmmn, (e) α-sheet, (f) β1 borophene. (d, g) Free energy diagram for
hydrogen evolution reactions. Reproduced from Ref. [155].

Fig. 10 (a) X-ray powder diffraction patterns and crystal structures of Mo2 B, α-MoB, β-MoB, and MoB2 . (b) Polarization
curves for amorphous B, Mo, Mo2 B, α-MoB, β-MoB, and MoB2 measured in 0.5 M H2 SO4 . IR-drop was corrected. (c) Stability
measurements (cyclic voltammetry) of β-MoB and MoB2 for the first and the 1000th cycle in 0.5 M H2 SO4 . The scan rate was
100 mV·s−1 . IR-drop was corrected. Reproduced from Ref. [159].

Fig. 11 Thermodynamic overpotentials (in V) for (a) ORR, and (b) OER activity as a function of Gibbs binding free
energies of reaction intermediates. Reproduced from Ref. [162].

4.6 Sensor a sensor for ethanol [167], formaldehyde [168] and hy-
drogen cyanide detection [169]. Non-equilibrium Green’s
Borophene shows a vast application prospect in gas sen- function (NEGF) and density functional theory (DFT)
sor. It has been reported that borophene can be used as method have been utilized to investigate the electronic

33403-13 Zhi-Qiang Wang, et al., Front. Phys. 14(3), 33403 (2019)

 Review article

properties of edge-hydrogenated 2D borophene. A sharp fast surface ion transport along the armchair direction has
increase in the current passing through the borophene been found due to the unique corrugated atomic struc-
device is found up on adsorption of ethanol molecules. ture of 2-Pmmn phase of borophene. Due to the polymor-
It is very similar that the electrical conductivity of phism, outstanding catalytic performances of borophene
B36 borophene significantly increases at the presence of have been found in hydrogen evolution reaction, oxygen
formaldehyde molecules, thereby generating an electrical reduction reaction, oxygen evolution reaction, and CO2
signal [168]. The electronic properties of hydrogen cyanide electroreduction reaction. This review gives a general view
absorbed B36 borophene adducts are strongly dependent of the stability, property, and application of borophenes.
on the molecular adsorption configuration. Furthermore, Before the practical application, some key issues should
B36 borophene is sensitive to the concentration of HCN be settled. Stability is one critical issue. Due to the high
gas. This finding shows that borophene can be used as the surface activity, borophene is prone to oxidation [51, 172].
sensor to detect some toxic gas. In addition, it is reported The covalent modification is effective to improve the sta-
that all-boron fullerene can be used as the CO and NO bility of borophene. It has been proved that hydrogenation
sensor [170]. The electronic structure, transmission func- can improve the stability of 2-Pmmn phase of borophene
tion and current-voltage of 2-Pmmn phase of borophene and the graphene-like borophene. Organic molecule ad-
with the CO, NO, NO2 or NH3 adsorption has been stud- sorption is a feasible approach to improve air-stability.
ied by DFT and NEGF simulations [171]. The results show Similarly, it has been reported that the adsorption of the
that the adsorption strength of CO, NO, NO2 and NH3 organic molecule on black phosphorus (BP) can improve
on 2-Pmmn phase of borophene surface is much stronger its air-stability. The polymer-BP composites preserve both
than that on graphene, MoS2 , and phosphorene. After the electron and hole mobility of pristine BP [173]. Further-
adsorption of CO, NO, NO2 or NH3 , impressive changes more, large-scale experimental growth is another issue.
of the transmission functions can be observed compared Now the experimental growth condition is too rigorous
to the pristine 2-Pmmn phase of borophene. Furthermore, to large-scale growth. Suitable growth temperature, pre-
gas adsorption induced detectable quenching of I–V fea- cursors and an atomically flat metal substrate need to be
tures, which can be regarded as OFF and ON states of determined for the chemical vapor deposition, which is the
the sensing mechanism, is observed. first choice for the synthesis of borophene [174]. Borophene
is usually synthesized on Ag/Al(111) surface. In practical
application, borophene has to be transferred to the desired
5 Summary and prospect substrate. The adhesion energy between the borophene
and substrate is weaker than that between silicene and
substrate. A manner similar to mechanical exfoliation of
In this review, we first introduce the experimental syn-
graphene for the transfer borophene to the desired sub-
thesis and theoretical prediction of borophene. The poly-
strate has been proposed by Yakobson’s research group
morphism of freestanding and the metal substrate sup-
[174].
ported borophene that is completely different from other
2D materials is particularly emphasised. A considerable
Acknowledgements This work was supported by the Fun-
number of borophene allotropes are reported whose forma-
damental Research Funds for Central Universities (Grant No.
tion energies are within a few meV/atom of the ground-
20720160020), Special Program for Applied Research on Super Com-
state. Borophene is also completely different from other
putation of the NSFC-Guangdong Joint Fund (the second phase)
2D materials because the distinction between borophene
under Grant No. U1501501, the National Natural Science Foun-
crystal and boron vacancy defect is blurry, due to the
dation of China (Grant Nos. 11335006 and 51661135011). This
ultralow defect formation energy. Then, we focus on the
work was also supported by China Scholarship Council (CSC NO.
physical and chemical properties of borophenes, mainly
201706310088).
including the mechanical, thermal, electronic, optical and
superconducting properties. We summarized the unique
properties of borophene, such as the negative Poisson’s References
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