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ChemPlusChem doi.org/10.1002/cplu.202000550

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3 Borophene: Current Status, Challenges and Opportunities
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5 Chuang Hou, Guoan Tai,* Zenghui Wu, and Jinqian Hao[a]
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1 Borophenes (2D boron sheets) have triggered a surge of tigation of their novel and fascinating physical properties. This
2 interest both theoretically and experimentally because of its report provides a brief review on theoretical and experimental
3 distinct structural, optical and electronic properties for exten- progress in borophene research. Some typical structures and
4 sive potential applications. Although theoretical efforts have properties of borophenes have been reviewed. The focus is laid
5 guided the research directions of borophene, only few synthetic on summarizing the experimental synthesis of borophene in
6 borophene sheets have been demonstrated experimentally. recent years, and on showing some ultrastable and semi-
7 Borophene sheets have been successfully synthesized exper- conducting borophenes which have been applied in electronic
8 imentally on metal substrates until 2015. Afterwards, more information devices. Finally, the future challenges and oppor-
9 efforts were put on the controlled synthesis of crystalline and tunities regarding experimental realization and practical appli-
10 semiconducting borophene sheets as well as on the inves- cations of borophenes are presented.
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1. Introduction planar boron clusters with multicenter bonding in the
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clusters,[19–21] which are viewed as the precursors to form the
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Since the boom of graphene,[1,2] other two-dimensional (2D) borophene. Subsequently, theoretical calculations show that
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materials such as black phosphorus (BP),[3] hexagonal boron the intermixing of hollow hexagons (HHs) and triangular lattice
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nitride (BN)[4] and transition metal dichalcogenides (TMDs),[5,6] in borophene,[22] such as α, β12, δ6 and χ3 boron sheets,[23] can
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have drawn dramatically increasing attention in recent years result in its structural planarity and higher stability than the
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owing to their novel optical, magnetic, electronic and thermal only triangular lattice. Excitingly, the hollow hexagons existing
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properties,[1–6] which are different from their bulk counterparts. in triangular lattice also renders significant structure diversity of
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All kinds of atomic-thick and crystalline materials have been borophene. With the deepening of theoretical research, a plenty
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already prepared in quantities experimentally. Thus, it promotes of unique physical and chemical properties in borophene have
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great potential applications of the 2D materials in electronic been reported, including highly anisotropic electronic structure,
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devices, energy storage and utilization. However, monoelemen- ultrahigh thermal conductance, mechanical compliance, pho-
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tal 2D materials represented by graphene have only a small non-mediated superconductivity and optical
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number in these families. Both theoretical calculations and transparency.[11–13,24–30] These properties make borophene be-
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experiments show that the 2D materials, such as silicene,[7] come an attractive material with potential applications in
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phosphorene,[8] arsenene,[9] and germanene[10] could not form memory, superconducting devices and flexible electronics for
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planar structure like graphene due to their out-of-plane quantum information technology.[29] Benefiting from extensive
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buckling with varying degrees. Whether there is a planar 2D theoretical and computational studies, our group first reported
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structure like graphene has always been an interest to be the successful preparation of 2D γ-boron monolayer on the
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expected. Boron (B), one of carbon’s nearest neighbors in the copper (Cu) surface by chemical deposition vapor (CVD).[24]
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periodic table of elements, is still among the most mysterious Almost at the same time, two independent groups grew 2D
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elements due to the severe electron-deficient bonding with boron sheets with different kinds on silver (Ag) in ultrahigh
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diversified chemical bonds, which ranges from the classical vacuum by molecular beam epitaxy (MBE) method.[29,30] After
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covalent two-center two electron (2c–2e) bonds and three- that, borophene sheets with different phases have been
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center two electron (3c–2e) bonds to multicenter bonds.[11–13] experimentally grown on the extensive substrates of Cu
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Since the end of the last century, boron nanostructures had (111),[31] Au (111)[32] and Al (111).[33] Recently, quasicubic boron
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been studied, which include zero-dimensional (0D) clusters and sheet with a direct bandgap,[34] crystalline semiconducting
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one dimensional (1D) nanotubes. 2D boron sheets, as the most boron quantum dots (BQDs),[35] and hydrogenated borophenes
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basic units for constructing the boron nanostructures, had (α’-4H-borophene)[36] have been successfully prepared in our
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attracted great attention in the past two decades.[14–36] group, which promote substantial potential applications of the
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Especially, Boustani, Ismail-Beigi and Yakobson et al. have boron nanostructures in next-generation nanoelectronics.
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systematically investigated stable 2D boron sheets, which guide However, the experimental realization of borophene is still
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the experimental growth of borophene.[14–16] After the discovery in its infancy, and more efforts on experiments and theories are
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of the planar hexagonal B36 cluster by the combination of expected to explore the structures and properties as well as
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theory and experiment, borophene, 2D boron monolayer, was growth mechanism of borophene. In this minireview, we first
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proposed by Wang’s group.[17,18] The group also reported the 2D introduce the structure and physical as well as chemical
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properties of borophene via theoretical prediction. Then, we
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mainly focus on the experimental synthesis progress of
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[a] C. Hou, Prof. G. Tai, Z. Wu, J. Hao borophene in recent years. Different from previous reviews, we
51 The State Key Laboratory of Mechanics and Control of Mechanical hope to remove set thinking and blaze new trails about the
52 Structures
Laboratory of Intelligent Nano Materials and Devices of Ministry of borophene field experimentally, guiding a feasible way to
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Education synthesize borophenes. Finally, we summarize the potential ap-
54 College of Aerospace Engineering plications of borophene. Theoretical and experimental pro-
55 Nanjing University of Aeronautics and Astronautics
Nanjing 210016 (P. R. China) gresses of borophene have been chronologically illustrated in
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E-mail: taiguoan@nuaa.edu.cn Figure 1.
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18 Figure 1. Major breakthroughs in boron nanostructures. Theoretical (top) and experimental (bottom) investigations are indicated, respectively.
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2. Structure and properties of borophene and can be expanded to obtain a stable two-dimensional boron
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structure: α-sheet (Figure 2b), but it is a high energy isomer.[11,12]
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2.1. Structure of borophene Afterwards, many other B80 buckyball structures were predicted
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to be much lower in energy.[37–39] However, the discovery of B80
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The successful discovery of graphene has ignited scientists to also promotes the unprecedented structural diversity of 2D
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search for other monoelemental 2D materials.[1] Boron, which is boron sheets. After that, numerous 2D boron sheets with
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similar to carbon in respect of physical properties, has been buckled and unbuckled structure have been predicted by ab
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extensively explored in recent year. Boustani et al. proposed initio calculations and the monolayers include β-sheet, γ-sheet,
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that bucked triangular motifs could form the most stable boron g1/8- and g2/15-sheet and so on.[23,40] The structures, which are
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structure (Figure 2a),[14] which led to the extensive studies of 2D composed of hexagonal holes and triangular patterns within
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boron sheets. As the theories progress, a novel 2D boron sheet, the triangular sheet, possess greater cohesive energies than
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which is different from the buckled triangular motif but more those without hexagonal holes. A global density parameter, η,
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stable, was observed. In 2007, Yakobson et al. reported that the is employed to describe their area densities and stability, which
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B80 buckyball composed of 20 hexagons and 12 pentagons is is defined as n/N, where n the number of the hexagonal holes
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analogous to the well-known C60 fullerene in shape and in a supercell consisted of N pristine triangular lattices.[11,15]
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symmetry.[37] Excitingly, the B80 buckyball is a beautiful structure
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39 Chuang Hou received his Bachelor’s degree Zenghui Wu received his Bachelor’s degree
40 from North University of China in 2018. He is from Wuhan University in 2014. Afterwards, he
currently a Ph.D. candidate in Prof. Guoan received his Master’s degree from Nanjing
41 Tai’s group. His research focuses on the syn- University of Aeronautics and Astronautics in
42 thesis and device application of borophene. 2019, and then joined Prof. Guoan Tai’s group
43 as a Ph.D. candidate in the same year. His
44 research interests focus on the epitaxial
45 growth and device applications of two-dimen-
sional materials.
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47 Guoan Tai received his Ph.D. from Nanjing Jinqian Hao received his Bachelor’s degree
48 University of Aeronautics and Astronautics, from Henan University of Technology in 2018.
49 and was a Postdoctoral Fellow in Department He is currently a Master’s candidate in Prof.
50 of Applied Physics at The Hong Kong Poly- Guoan Tai’s group. His research interests focus
51 technic University. He is currently a full on synthesis and device applications of boron
professor in College of Aerospace Engineering nanostructures.
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at Nanjing University of Aeronautics and
53 Astronautics. His research interests focus on
54 the photodetectors and sensors based on 2D
55 materials, energy storage and conversion
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the substrates could promote 2D boron sheets nucleation and

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donate extra electrons to stabilize the sheets, which caused the
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preferred β12-sheet (η = 1/6) as the ground state. Excitedly, the
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predicted results have been confirmed by the corresponding
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experiments.[30] Surface functionalization is another feasible
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approach to stablilize the structure of borophene.[13] Among the
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surface functionalization methods, hydrogenation has been
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proved to be a feasible way to stabilize the structure of 2D
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materials and open their band gaps.[43–45] Remarkably, several
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months ago, our group not only predicted some more stable
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α’-borophene after hydrogenation theoretically, but also veri-
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fied the rationality of the structure experimentally.[36]
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2.2. Properties of borophene
15 Figure 2. Typical structures of 2D boron sheets. a) A buckled triangular
16 lattice with hexagonal pyramids.[14] Reproduced from reference [12] with
permission from Royal Society of Chemistry. b) The B80 buckyball inves- Since boron has severe electron-deficiency behavior and tends
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tigated by Szwacki et al.[37] The buckyball can be expanded to obtain a stable to form a diversity of multicenter bonds, borophene possesses
18 2D boron structure: α-sheet. Reproduced from reference [14] with permis- a number of unique and desirable physical properties. Mortaza-
19 sion from Wiley-VCH. c) A stable 2D β12 sheet on Ag was predicted.
Reproduced from reference [40] with permission from Wiley-VCH. d) 2D χ3 vi et al. first proposed vacancy defect of borophene affecting
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boron sheet on Ag (111). Reproduced from reference [30] with permission the mechanical properties.[46] It was confirmed that the Young’s
21 from Nature Publishing Group. modulus values of synthesized β12 and χ3 sheets are up to 179.0
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and 198.5 N/m along the armchair direction, respectively. More-
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over, defect-free 2-Pmmn, which has larger Young’s modulus
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Ismail-Beigi et al. predicted that the α-sheet of boron with a (398 N/m) than that of β12 and χ3, shows a negative Poisson’s
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B1/9 structure,[15] which has the highest cohesive energy per ratio that is completely different from other reported 2D
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atom among all of the 2D boron sheets, may be the best materials.[47]
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candidate for reported flat and stable boron sheet. Subse- Most of 2D boron sheets reported are metallic in both
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quently, Yakobson et al. proposed numberous 2D boron sheets previous theoretical predictions and experimental observations.
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with good stabilities using a cluster-expansion method, and Based on the local density approximation (LDA), Penev et al.,
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predicted two novel 2D boron sheets with a value of η = 1/8 predicted that the metallic states of β12 and χ3 sheets were
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and 2/15, which were named as B1/8- and B2/15-sheet (Fig- originated from the 2px and 2py states, which resulted in the
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ure 2c,d).[40,41] In addition, buckling or forming multilayer can appearance of band gap with close to the Fermi level in the
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also gain energy to stabilize 2D flat boron sheet. In 2012, Wu boron sheets with the values of η = 10 ~ 15 %.[22] Experimental
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et al. explored using PBE0 and PBE calculations that the α-sheet measurements by angle-resolved photoemission (ARPES) are
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with slightly buckling named α’-sheet can remove the negative well consistent with the predicted results.[48] Graphene can host
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frequencies and it has a higher cohesive energy than the α- massless Dirac fermions with a significant Berry phase,[49] thus
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sheet.[23] However, free-standing borophene sheets was pre- showing a huge potential for electronic application. Strikingly,
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dicted to be unstable dynamically.[11] The instability is resulted motivated by Dirac cones of borophene in theory,[50] Feng and
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from the high reactivity of borophene, which will bring many Gupta et al. found that β12 sheet, which was similar to graphene
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challenges in real applications. Various methods were proposed in a way, also hosted the Dirac cones.[48,51]
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to improve the stability of borophene such as stable adsorption Our group has successfully investigated the γ-B28 and α’-
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on the substrate and surface functionalization.[11–13,40–45] To borophene after hydrogenation and found that the boron
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promote the experimental realization and stabilize the structure sheets could be opened up the bandgap to form semiconduct-
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of 2D boron sheets, metal substrates are regarded as an ing materials.[24,36] Meanwhile, the optical properties in the
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effective strategy to solve the stability of the sheets. Liu et al. boron sheets were also observed by UV-vis absorption and
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found that synthesis of 2D boron sheet could be realized by photoluminescence (PL) spectroscopies.
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depositing boron sources on Au, Cu and Ag or metal boride Thermal conductivity as an another important physical
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(MgB2) substrates.[16] Zhao et al. proposed the growth mecha- parameter has been studied in borophene.[11–13,52] The diversity
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nism and hole formation of 2D boron sheet from the clusters of of borophene structures leads to the different forms of thermal
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boron on Cu (111).[42] Furthermore, it was also reported that the conductivity. For isotropic α-sheet borophene, the thermal
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hexagonal hole can form easily during the nucleation of 2D conductivity is 1.43 nWK 1 nm 2. The high-frequency phonon
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clusters, which is essential for the subsequent theoretical modes mainly dominate the thermal transport of borophene,
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prediction. In 2015, Zhang et al., using the cluster expansion which is completely different from the other monoelemental 2D
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method, systemically investigated 2D boron sheet which is materials.[53,54] Besides, the thermal conduction of most of other
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composed of hexagonal holes and triangular patterns on Ag, Ni, borophenes is anisotropic. For example, the thermal conductiv-
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Au and Cu ordinarily used in CVD growth.[40] They indicated that ities of β12 are ~ 3.30 and 10.97 nWK 1 nm 2 along the armchair
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and zigzag directions, respectively. Thus, it was found that produce the diboron dioxide (B2O2) vapor. Temperature of T1
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borophene possessed a near extraordinary thermal conductivity was set to 1100 °C. The large-area boron monolayer was
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as graphene. Additionally, Yakobson, et al. have systematically prepared on a scalable copper (Cu) foil at 1000 °C (T2) for 1 h, as
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investigated superconducting property of borophene using shown in Figure 3d,e.
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first-principles calculations.[50] Remarkably, they found that all The fast Fourier transform (FFT) and high-resolution trans-
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types of stable borophenes showed superconductivity. How- mission electron microscopy (HRTEM) images clearly revealed
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ever, the experimental investigation on the desirable properties that the structure of the monolayer was consisted of icosahe-
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of borophenes are still rare. More effects on experimental dral B12 units and B2 dumbbells. It belongs to orthorhombic γ-
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realization to enrich and verify the properties of borophene are B28 structure with a unit cell of 28 atoms, where a = 5.054, b =
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urgently expected. 5.620 and c = 6.987 Å, and a space group of Pnnm. Figure 3c
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gives a clear view in bc projection to observe the polyhedral
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structure of the basic unit cell of the monolayer. The thickness
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3. Experimental realization of borophenes of the boron monolayer tested by atomic force microscopy
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(AFM) is close to 0.80 nm (Figure 3f) which is close to the a-axis
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Although the possible experimental synthesis of borophene on height of the γ-B28 model (a = 0.5054 nm) (side view of Fig-
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various metal substrates was confirmed theoretically, only a few ure 3c), which suggests that the prepared sheet is monolayer.
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types of 2D boron sheets have been very recently prepared The binding energy of the B1s spectrum is fitted to a single
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experimentally. The boron monolayer was firstly prepared by peak located at 187.6 eV, which is attributed to the B B bond
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our group via a home-made two-zone chemical deposition (Figure 3g). Moreover, the optical band gap measured by UV-vis
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vapor (CVD).[24] The growth procedure of the boron monolayer absorption spectroscopy is around 2.25 eV (Figure 3h) which
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is schematically demonstrated (Figure 3a–c). During the experi- was near to the theoretical value (2.07 eV), and strong photo-
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ment, the temperatures of the source (T1) and substrate zone luminescence was observed (Figure 3i), which reveals that the
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(T2) were controlled separately to obtain the precise growth monolayer is a promising semiconductor.
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rate. The mixture of B and B2O3 powders was selected as a During the same period, Guisinger et al. and Feng et al. in
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boron source and hydrogen (H2) gas was as a carrier gas to two independent groups fabricated different kinds of boro-
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53 Figure 3. Experimental realization of 2D γ-B28 monolayer grown on Cu. a) Schematic representation of the 2D γ-B28 monolayer using a home-made two-zone
54 CVD. b) Top and side view of the 2D boron structure model. Unit cell vectors are shown. c) The basic polyhedral structure of the sheet shown in bc projection.
55 d) Optical image of the boron monolayer on the Cu foil. A photograph of the monolayer on the Cu foil is shown in the right top corner. e) Optical image of
the monolayer transferred onto a SiO2/Si substrate. f) A typical AFM image of the monolayer obtained on the SiO2/Si substrate. g) XPS analysis of the B1s peak
56 of the monolayer. h, i) UV-Vis and PL spectra of the γ-B28 monolayer. Reproduced from reference [24] with permission from Wiley-VCH.
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phene structures in ultrahigh vacuum.[29,30] Single-crystal and was labeled as S1 phase (Figure 4e). As the temperature was
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clean Ag (111) surface was used as the growth substrate, and raised to 680 K, another S2 phase which was composed of
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borophene was deposited from a high-purity boron source with parallel chains could be obtained (Figure 4f). Moreover, the S1
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a highly controlled condition using the molecular beam epitaxy phase could also be transformed into the S2 at 650 K (Fig-
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(MBE) technique. Guisinger et al. observed three types of phase, ure 4g). STM results further confirmed that the borophenes
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homogeneous phase, stripped phase and nanoribbons, at were consistent with β12 and χ3 sheets predicted previously by
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substrate temperature of 550 °C (Figure 4a).[29] Large-scale Zhang et al.[40] Similarly, the two boron sheets have the metallic
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scanning tunneling microscope (STM) topography images show characteristics.
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that the borophene is atomically thin and has hundreds of Subsequently, Wu et al. employed low-energy electron
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nanometers in horizontal size (Figure 4a,b). STM also reveals microscopy (LEEM) to monitor the nucleation and growth of the
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that the deposition rate and substrate temperature determine boron sheets on Cu (111) substrate in real time (Figure 5a).[31] A
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collectively proportions of each structure. A low deposition rate self-made electron beam evaporation source device was used
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is favorable to the flat striped phase consisted of rectangular to control the deposition rate of boron as 0.05 ML · min 1. Two-
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lattices without hollow hexagons (Figure 4c), while a high dimensional boron with a size of 10–100 μm2 was synthesized
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deposition rate may render the appearance of a homogeneous on a Cu (111) substrate at 770 K (Figure 5a), and a new
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phase (Figure 4d). Furthermore, the flat phase will transform triangular network structure with a vacancy concentration of
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into a new corrugated striped phase with the increase of the η = 1/5 was obtained, as shown in Figures 5b–d. They also
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temperature. However, both of boron sheets show the metallic repeated the previous work of the borophene on the Ag
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characteristics unlike bulk boron allotropes. substrate and found that the single crystal domain size was
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Other parallel work reported by Feng et al. two different only a few tens of nanometers. Thus, high nucleation density
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structural phases of borophene.[30] The borophenes showed a on the Ag surface and the tendency of boron aggregation
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triangular lattice with different concentrations of hollow limited its size. At the same time, the interaction between the
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hexagons. They found that there were only disordered borophene and the substrate was studied, and it was found
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structures or clusters on the surface when the substrate that the charge transfer occurred between borophene and the
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temperature was below 500 K. When the temperature was substrate but there was no significant covalent bonding. This
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increased to 570 K, it was observed that rectangular lattices work demonstrates that the growth mechanism of borophene
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with parallel atomic rows were tested in the STM image, which is a self-limiting process, which is very beneficial to the
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formation of atomic thin-layer heterojunctions.
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Figure 4. Experimental formation and related structural characterization of
44 different phase borophenes on Ag (111) in two independent groups. a,b)
45 Large-scale STM images of borophene reveal low and medium coverages at
46 different temperatures. Red, blue and white arrows represent regions of
homogeneous-phase, striped-phase nanoribbons and striped-phase islands,
47 respectively. c) STM images for the atomic-scale striped phases
48 (Vsample = 0.1 V, It = 1.0 nA). Flat region exists in the corrugated region. A
49 rectangular lattice is shown in the inset. d) STM images for atomic-scale
homogeneous phase (Vsample = 0.1 V, It = 1.0 nA). Reproduced from refer- Figure 5. Experimental realization of borophene on the Cu (111) surface. a)
50 ence [29] with permission from American Association for the Advancement Real-time nucleation process of borophene at T = 770 K observed by the
51 of Science. e) After the Ag substrate was heated from room temperature to sequence of bright-field LEEM, showing that the suitable position along
52 about 570 K, topographic image of borophene sheets was characterized by down-step edge of Cu (111) terraces and the fast growth speed along the
STM. The borophene islands are named as ‘S1’ phase. f) High-magnification step-edge direction. b) Ultrahigh-magnification STM image of borophene. c)
53 STM image of another phase (S2). g) STM image of borophene after DFT-simulated STM data, which is in good agreement with that of the
54 increasing the temperature up to 650 K. The two different phases: ‘S1’ and experiment. d) Top view of the borophene model structure with green
55 ‘S2’. Most boron islands tend to transform to the S2 phase, but a small boron atoms and bonds. The regular zigzag motif with red dashed lines
number of the islands with the S1 phase still remains. Reproduced from existing in (b) and (c). Reproduced from reference [31] with permission from
56 reference [30] with permission from Nature Publishing Group. Nature Publishing Group.
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Kiraly et al. selected Au (111) substrates to grow borophene minimize the energy, resulting in the formation of nanoscale
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via MBE, because it is one of the low-energy metal surfaces that borophene islands (Figure 6a,b). Moreover, the islands, which
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can be reconstructed to realize low surface energy.[32] Unlike the were confirmed by atomic-resolution imaging, are consistent
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growth process on the Ag substrates, boron atoms diffuse into with a calculated v1/12 boron structure nucleated at the network
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Au at high temperature and separate to the surface of the nodes (Figure 6c). When the concentration of boron was
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substrate to form the islands of the boron sheets when the increased, the trigonal network broke down which resulted in
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substrate is cooled. In the initial stage of the growth of low- the appearance of larger-scale borophene islands. Thus, the
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concentration boron, Au (111) reconstructs trigonal networks to domains will extend at least several tens of nanometers due to
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the increase of boron dose. Like borophene grown on other
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metal substrates via MBE, the one on Au (111) surface is also
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metallic.
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Although much progress has been made in experiments,
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the stability of borophene sheets grown under ultra-high
13
vacuum is still a huge challenge. Moreover, the metallic
14
character of borophene dramatically also hinders its extensive
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applications in nanoelectronic devices. Thus, the preparation of
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crystalline semiconducting borophene sheets with stable
17
structure is necessary to high-performance nanoelectronics and
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optoelectronics. Along this direction, our group has successfully
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prepared ultrastable crystalline semiconducting hydrogenated
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borophenes in a hydrogen-rich atmosphere.[36] Under a control-
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lable condition, the borophenes were realized experimentally
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without any metal substrates using a three-step heating
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procedure in the condition of in-situ thermal decomposition of
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sodium borohydride (NaBH4). First, the NaBH4 powders was
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annealed to 490 °C to obtain an initial intermediate. Second,
26 Figure 6. Experimental measurement of borophene on Au (111). a) STM
increasing the temperature to 550 °C, a more stable intermedi-
27 image of a superclean Au (111) surface before the deposition of boron
(V = 1.5 V, I = 100 pA). b) Structure of a herringbone reconstruction ate was formed. Third, large-scale hydrogenated borophenes
28
changed to a trigonal network at the boron deposition temperature of can be obtained when the intermediate was ramped to 600 °C.
29 550 °C, where borophene islands with nanoscale (an area selected with a
The borophenes, with thickness of less than 1 nm, can be
30 white dashed line) form at the nodes, rendering templated growth across
the Au (111) surface (V = 0.1 V, I = 200 pA). c) Atomic model structure of observed by magnification SEM image, as shown in Figure 7a.
31
the v1/12 borophene and the corresponding structure on Au (111) given by The average lateral size, which is statistically analyzed, is close
32 theoretical calculations. (Left, top view; right, side view). Reproduced from
to 5.14 μm. Atomic force microscopy (AFM) displays that the
33 reference [32] with permission from American Chemical Society.
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51
52
Figure 7. Experimental realization of ultrastable crystalline semiconducting hydrogenated borophene. a) SEM image of the hydrogenated borophenes. b) AFM
53 image of the borophene. The inset shows height analysis along the red line, indicating a thickness of around 0.78 nm. c) Low-magnification TEM image of the
54 borophene. d) HRTEM image of the borophene. The inset shows the corresponding SAED image. e) HRTEM image obtained by masking the FFT pattern
55 extracted from the red rectangular region in (d). f) HRTEM image extracted from (e). The inset shows the corresponding calculation model. g) XPS analysis of
B1s peak of the borophenes. h) PL spectrum of the borophenes. The red line is the corresponding Gaussian fit. i) I–V characteristics of the borophene-based
56 memory device. Reproduced from reference [36] with permission from Wiley-VCH.
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thickness of a typical borophene is around 0.78 nm (Figure 7b).

1
A typical transmission electron microscopy (TEM) image reveals
2
that the borophene with a lateral size of over 10 μm is covered
3
onto the holes of the TEM grid (Figure 7c). The borophene is a
4
single crystal, which was characterized through HRTEM image
5
and the corresponding selected-area electron diffraction (SAED)
6
pattern. A HRTEM image, which is extracted from the red
7
rectangular region in Figure 7d, is reconstructed by masking the
8
two-dimensional FFT pattern (Figure 7e,f), and the correspond-
9
ing lattice spacings of around 4.31 and 4.36 Å which is in good
10
agreement with α’-sheet bonded by 4 hydrogen atoms (α’-4H-
11
borophene) with a value of η = 1/9.
12
The characteristic peaks of high-resolution B1s spectrum
13
located at 187.6 and 188.2 eV show that two types of bonding
14
structure happen in different chemical environments (Fig-
15
ure 7g). After the treatment of the borophenes in strong acid or
16
base solvents for over 48 hours, the XPS spectra of the Figure 8. Experimental realization of quasicubic boron sheet. a) A typical
17
borophenes are in good agreement with that of the original low-magnification TEM image of quasicubic boron sheet. The corresponding
18 SAED image is shown in the right top corner. b) HRTEM image extracted
ones, showing that the borophenes are superior chemical
19 from the red rectangular region in (a). The corresponding HRTEM map is in
stability due to the surface hydrogenation. Furthermore, the good agreement with the calculation model along the [011] direction shown
20
borophenes can withstand the temperature of 400 °C in air and in the right top corner. c) High-resolution XPS analysis of the B1s peak of the
21 boron sheet. d) PL spectra of the boron sheets and bulk β-rhombohedral
1000 °C in Ar gas, suggesting its superior thermal stability. The
22 boron. A 325 nm laser is used. The green line represents the corresponding
optical band gap (Eg) of the borophenes was estimated to be Gaussian function fitting. Reproduced from reference [34] with permission
23
2.48 eV by UV-Vis spectrum, which was excellent consistent from Royal Society of Chemistry.
24
with 2.49 eV phonon energy observed by PL spectrum (Fig-
25
ure 7h). Finally, a memory device based on the borophenes was
26
fabricated to show their applications in high-performance
27
electronic devices (Figure 7i). Thus, the chemical and thermal flocculent boron powder of 30 mg and acetonitrile of 15 mL
28
stability under environmental conditions is very exciting and was respectively added into a three-necked bottle before the
29
bodes well for its potential wide applications. The fact that the probe ultrasonication process. In the feasible probe sonication
30
borophene is a semiconductor, suggests that it may be even process (Figure 9a), an ultrasonic probe with 10 mm in diameter
31
more important than graphene in nanodevice and nanoelec-
32
tronic applications.
33
Furthermore, quasicubic boron sheets has been synthesized
34
on Ni foil via CVD in our group.[34] The prepared 2D boron
35
sheets with a quasicubic structure have been observed by
36
HRTEM (Figure 8a,b), which is in excellent agreement with
37
theoretical prediction based on first-principles calculations.
38
Moreover, the results show a novel and cubic 2D boron
39
structure which completely differs from the reported boron
40
bulk structures and 2D boron sheets. The XPS result confirms
41
that the boron sheets are stable in air, as shown in Figure 8c.
42
Furthermore, PL spectrum in Figure 8d shows that the boron
43
sheets are semiconducting with a 2.4 eV bandgap, which are
44
further predicted by the theoretical calculation. The structure
45
and property of the boron sheets will enrich and perfect those
46
of the reported 2D boron sheets and be able to have
47
unprecedented diversity in monoelemental 2D materials with
48 Figure 9. Experimental realization of crystalline semiconducting boron
substantial potential applications for sensing, optoelectronic quantum dots (BQDs). a) Schematic diagram of the fabrication of the BQDs.
49
and nanoelectronic device. b, c) Typical TEM image and HRTEM image of the BQDs. The inset in (b)
50 shows that lattice spacing of a BQD is about 0.181 nm, which is consistent
Following by the borophene progress, boron clusters are
51 with the atomic model structure of the BQD along (024) orientation. d) A
considered as an unit for forming 2D borophene,[55] our group Gaussian distribution curve of lateral and uniform size distribution of BQDs.
52
also first reported that large-scale and crystalline boron e) UV-Vis spectrum of the BQDs. f) PL spectra of BQDs and the boron powder
53 tested by 325 nm laser at room temperature. The corresponding PL
quantum dots (BQDs) with semiconducting nature were synthe-
54 spectrum of boron powder with black line is shown in the right top corner.
sized successfully by a facile and efficient probe ultrasonic g) Current-voltage (I–V) characteristics of the BQDs-based memory device.
55
approach using the flocculent boron powders in acetonitrile The diagram schematic of the device is shown in the inset. Reproduced from
56 reference [35] with permission from American Chemical Society.
solution.[35] To obtain the crystalline BQDs, the commercial
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were used, the ultrasonic power was set to 400 W, and

1
frequency and ultrasonic time were respectively controlled at
2
20 KHz and 60 min. After the centrifugation of the resultant
3
solution at 1500 rpm for 60 min, BQDs can be observed in
4
supernatant. A TEM image shows a mass of ultrasmall and
5
uniform BQDs (Figure 9b). As shown in Figure 9b,c, the
6
crystalline BQDs with highly paralleled lattice fringes were
7
observed in HRTEM images. The lattice distance of the BQDs is
8
in well consistent with the (024) lattice spacing of the α-
9
rhombohedral bulk boron (PDF: 78-1571), demonstrating the
10
BQDs are originated from the α-rhombohedral boron. More-
11
over, the average lateral size and the diameter of BQDs
12
concentrate on around 2.5 nm through the statistical analysis,
13
which conforms to the distribution curve of Gaussian fitting
14
(Figure 9d).
15
The optical bandgap of the as-prepared BQDs was charac-
16
terized by UV-vis absorption spectroscopy. As shown in Fig-
17
ure 9e, the optical bandgap is calculated to be 2.45 eV, which is
18
well consistent with the photon energy (2.46 eV) observed by
19
the room-temperature PL spectrum (Figure 9f). Meanwhile, the
20
fabricated BQDs-based device displays a nonvolatile rewriteable
21
memory effect with a low operating voltage and high ON/OFF
22 Figure 10. Potential applications of borophene. a) Schematic setup of the
switching ratio (Figure 9g).
23 borophene gas sensor. The insert is current-voltage (I–V) characteristics for
borophene monolayer with and without adsorbed gas molecules. Repro-
24
duced from reference [58] with permission from American Chemical Society.
25 b) Schematic illustration of the borophene-based memory device. Repro-
4. Potential applications of borophene duced from reference [36] with permission from Wiley-VCH. c) CV curves of
26
boron sheets based supercapacitor at a scan rate of 10 mV/s. Reproduced
27
The excellent physical properties of borophene render it as an from reference [62] with permission from American Chemical Society. d)
28 Modulated pump and out light profiles of MZI configuration at output 1 and
expected material with potential applications in sensing, nano-
29 2. Reproduced from reference [63] with permission from Wiley-VCH. e) The
electronic and optoelectronic devices and high-efficiency en- photonic drug delivery platform based on boron sheets with photothermal
30
ergy storage technologies. Theoretically, borophene, the light- conversion efficiency of 42.5 %. Reproduced from reference [64] with
31 permission from Wiley-VCH. f) Tafel plots of Mo3B films (Log current versus
est 2D metal material, can be viewed as one of the most ideal
32 potential). Reproduced from reference [65] with permission from Royal
materials for energy storage.[56,57] For example, the interaction of Society of Chemistry.
33
H2 with borophene is similar to that of graphene, but the
34
capacities of hydrogen storage for borophene is larger than
35
that of graphene. It has also been investigated that the alkali
36
metals (AM=Li, Na, and K) atoms existing on the 2D boron sheet Few-layered B sheets prepared by ultrasound-assisted
37
remarkably increase the binding energies and storage capacities liquid-phase exfoliation were used as supercapacitor electrode
38
for hydrogen.[57] Motivated by the study of graphene sensors to materials. As shown in Figure 10c, the fabricated device shows
39
detect individual gas molecules, the absorptions of CO, NH3, a desirable and impressive electrochemical performance.[62] Guo
40
CO2, NO and NO2 on borophene surface were calculated by et al. exploited all-optical signal processing of liquid-exfoliated
41
first-principles calculations.[58] It has been noted that the bind- boron nanosheets that was mediated by its superior photo-
42
ing of the target gases on the borophene surface is quite thermal response. The stable all-optical modulator exhibits fast
43
strong. Strikingly, binding energies of gas molecules on response speed and high modulation efficiency (Figure 10d).[63]
44
borophene are far stronger than those on other reported 2D Besides, it was reported that a new drug delivery platform
45
materials such as graphene, MoS2 and phosphorene.[59–61] Thus, based on the PEGylated boron nanosheets has been reported,
46
it was predicted that borophene was a potentially ideal material which showed a plenty of substantial promising features for
47
for nanoscale gas sensor, as shown in Figure 10a. imaging and cancer therapy.[64] For example, it showed a
48
Experimentally, borophene with semiconducting character superior near-infrared photothermal conversion with an effi-
49
prepared by our group has been successfully applied in ciency of up to 42.5 % (Figure 10e). The report not only presents
50
memory devices (Figure 10b).[36] The results indicate that the a novel strategy to prepare few-layered B nanosheets, but also
51
device has an ultralow switching voltage of less than 0.4 V, provides a useful and robust 2D platform for all kinds of
52
suggesting that it has potential applications in future electronic biomedical applications.
53
information devices with a low-energy consumption. Thus, the Furthermore, the boron element has been employed as a
54
memory device shows higher performance than those based on basic unit to form new compound 2D materials. Our group
55
other 2D materials. reported that ultrathin crystalline Mo3B films were synthesized
56
on molybdenum foils by chemical vapor deposition.[65] The
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ultrathin Mo3B films exhibit outstanding catalytic performance potential device applications. Just as the device demonstrations
1
in hydrogen evolution reaction (HER) (Figure 10f), and super- mentioned in this review, borophene has been tried as chemical
2
long cycling stability as well as outstanding resistance to sensors, nonvoltaic memory device, supercapacitor, electro-
3
corrosion. chemical hydrogenation production, and cancer therapy and
4
Therefore, borophene is being developed for potential imaging. More importantly, the applications regarding ad-
5
applications in electronic information, electrochemistry and vanced information storage devices, photodetectors and sen-
6
biomedicine, which may open a door for its real device sors still remain relatively unexplored. So, we believe that there
7
applications. are still many fascinating properties and device applications to
8
be explored.
9
Although some progress has been made, the research of
10
5. Summary and outlook borophene is still in its infancy. This is a research field where
11
both challenges and opportunities coexist, and it requires
12
In summary, boron with severe electron deficiency behavior systematic and in-depth exploration for preparation, properties
13
results in structural diversity and complexity for boron nano- and applications of borophene. Specially, the controlled syn-
14
structures. After the discovery of graphene, theoretical studies thesis of crystalline and semiconducting borophene like α’-4H-
15
for boron has been also focused on 2D boron sheet – borophene needs more efforts to explore more kinds of novel
16
borophene. Thus, some possible borophene structures have and fascinating physical properties. We hope this minireview
17
been searched, and then a plenty of unique physical properties, can remove set thinking and blaze new trails about the
18
such as mechanical compliance, highly anisotropic electronic borophene field theoretically and experimentally. Therefore, we
19
structure, optical transparency, ultrahigh thermal conductance have every reason to believe that borophene can open up
20
and phonon-mediated superconductivity, were quickly inves- plenty of possibilities to lead the research and development of
21
tigated. Meanwhile, the feasible strategies to synthesize the the fantastic 2D materials.
22
borophenes were also proposed by the theoretical studies.
23
Subsequently, three independent groups have successfully
24
reported different 2D boron sheets on metal substrate by CVD Acknowledgements
25
and MBE almost at the same time. Recently, using the MBE
26
method, some different borophene structures were also realized This work was supported by the National Natural Science
27
experimentally on other metal substrates. However, the struc- Foundation of China (61774085), Natural Science Foundation of
28
tural instability and the metallic nature of the boron sheets limit Jiangsu Province (BK20151475), Six Talent Peaks Project in Jiangsu
29
seriously their applications in nanoelectronic and optical Province (XCL-046), the Research Fund of State Key Laboratory of
30
devices. Therefore, the preparation of ultrastable semiconduct- Mechanics and Control of Mechanical Structures (NUAA) (MCMS-I-
31
ing borophenes is a prerequisite for the borophene application 0420G02) and the Priority Academic Program Development of
32
towards advanced nanoelectronics and optoelectronics. Jiangsu Higher Education Institutions.
33
To stabilize the structure of the borophenes, some effective
34
strategies, such as bulking, hydrogenation and substrate
35
assistance, are proposed. A number of unique and desirable Conflict of Interest
36
physical properties are predicted systematically. Experimentally,
37
some progresses of borophene synthesis via CVD and MBE have The authors declare no conflict of interest.
38
been made, but stable semiconducting borophenes are still
39
very limited. So, the development of large-area controllable Keywords: boron sheets · borophene · monolayers ·
40
preparation of stable semiconducting borophene is extremely semiconductors · two-dimensional materials
41
necessary to meet the requirement of vital application in
42
boron-based nanoelectronic and optoelectronic devices. The
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